CN104804276B

CN104804276B - High molecular weight polyethylene powder, microporous barrier and high strength fibre

Info

Publication number: CN104804276B
Application number: CN201410043341.7A
Authority: CN
Inventors: 加茂弘; 藤原昭夫; 马原忠典; 片冈和义
Original assignee: Asahi Kasei Kogyo KK
Current assignee: Asahi Kasei Corp
Priority date: 2014-01-29
Filing date: 2014-01-29
Publication date: 2018-07-17
Anticipated expiration: 2034-01-29
Also published as: CN108752607A; CN104804276A; CN108752607B

Abstract

The present invention relates to High molecular weight polyethylene powder, microporous barrier and high strength fibres.It is an object of the invention to obtain, Continuous maching productivity is excellent, High molecular weight polyethylene powder of product size excellent in stability.A kind of polyethylene powder, wherein the content for the aluminium hydroxide that minor axis is 50 μm or more is 10 in polyethylene powder 500g hereinafter, and viscosity average molecular weigh is 100000 or more.

Description

High molecular weight polyethylene powder, microporous barrier and high strength fibre

Technical field

The present invention relates to High molecular weight polyethylene powder, microporous barrier and high strength fibres.

Background technology

High molecular weight polyethylene powder is for various use such as film, thin slice, microporous barrier, fiber, foaming body, pipes On the way.Especially as using lead accumulator and lithium ion battery as the diaphragm microporous barrier and high strength fibre of the secondary cell of representative Raw material, use High molecular weight polyethylene powder.As the reasons why using High molecular weight polyethylene powder, molecular weight can be enumerated Height, therefore stretch process is excellent, intensity is high, and chemical stability is high, and long-term reliability is excellent etc..

The general viscosity of these High molecular weight polyethylene powders is high, it is difficult to is processed by injection moulding etc., therefore mostly It is dissolved into solvent and is formed.In general, when manufacturing secondary battery membrane microporous barrier or high strength fibre etc., it is high Molecular weight polyethylene powder is for example kneaded in the state of being dissolved into solvent at high temperature in an extruder.As in this way Obtained microporous barrier, for example, disclosed in Patent Documents 1 to 3 foreign matter (polyethylene gel) in film less, as the spy of battery The excellent microporous barrier of property.

In patent document 1, it is 70ppm polyolefin microporous membranes below to disclose aluminium content, discloses and thus reduces Foreign matter (polyethylene gel) in film, improves the cycle characteristics of battery.

In patent document 2, it discloses and contains being manufactured using organo-aluminum compound as co-catalyst for specific quantity The polyolefin microporous membrane of polyethylene discloses the cycle characteristics of the foreign matter, battery that thus improve in film.

In patent document 3, it is 20ppm polyolefin systems below to disclose aluminium ratio shared in polyolefin composition The manufacturing method of microporous barrier discloses the cycle characteristics of the foreign matter, battery that thus improve in film.

In recent years, the demand growth of especially secondary battery membrane microporous barrier and high strength fibre is notable, strong it is expected Further increase productivity and low cost production.It, can be with it is expected that do not stop extruder etc. from the viewpoint of improving productivity Continuously steady production (Continuous maching productivity is excellent).

In addition, for secondary battery membrane microporous barrier and high strength fibre, examined from the viewpoint of long-term reliability Consider, product size (film thickness, fibre diameter etc.) is important characteristic, is strongly desired to stably obtain these characteristic (product sizes Excellent in stability).

Existing technical literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2011-233542 bulletins

Patent document 2：No. 4822567 bulletins of Japan Patent

Patent document 3：Japanese Unexamined Patent Publication 2011-74119 bulletins

Invention content

Problem to be solved by the invention

For continuously steady production microporous barrier and high strength fibre, the spy of the High molecular weight polyethylene powder as raw material Property is also important.But in Patent Documents 1 to 3, although having note for the foreign matter (polyethylene gel etc.) in microporous barrier It carries, but it is not open for the characteristic of the polyethylene powder as raw material.

In addition, the film thickness of the Continuous maching productivity and microporous barrier etc. whens for manufacture microporous barrier and high strength fibre etc. Stability, fibre diameter stability of high strength fibre etc. are not recorded, and are not also had for the means for improving these characteristics It records.

The present invention foundes in view of the above problems, and its object is to obtain, Continuous maching productivity is excellent, product size is steady Qualitative excellent High molecular weight polyethylene powder.

The means used to solve the problem

Therefore, the present inventor is to realize that aforementioned problems have carried out research extensively and profoundly, as a result, it has been found that, contain specific The aluminium hydroxide of several specific dimensions and the polyethylene powder with specified molecular weight, Continuous maching productivity is excellent, and And product size excellent in stability.

That is, the present invention is as described below.

[1] a kind of polyethylene powder, wherein

The content for the aluminium hydroxide that minor axis is 50 μm or more be in polyethylene powder 500g 10 hereinafter, and

Viscosity average molecular weigh is 100000 or more.

[2] the polyethylene powder as described in preceding paragraph [1], wherein

Aluminium element content is 0.2ppm or more.

[3] the polyethylene powder as described in preceding paragraph [1] or [2], wherein

Polyethylene powder contains the aluminium hydroxide that minor axis is less than 50 μm.

[4] the polyethylene powder as described in any one of preceding paragraph [1]~[3], wherein

Aluminium element content is 0.2ppm or more, and magnesium element content is 0.5ppm or more and 12ppm or less.

[5] the polyethylene powder as described in any one of preceding paragraph [1]~[4], is used for secondary battery membrane.

[6] the polyethylene powder as described in preceding paragraph [5], is used for lithium ion secondary battery membrane.

[7] a kind of microporous barrier is obtained by by the polyethylene powder processing described in any one of preceding paragraph [1]~[6].

[8] the polyethylene powder as described in any one of preceding paragraph [1]~[4], is used for high strength fibre.

[9] a kind of high strength fibre, by will be such as the polyethylene powder as described in preceding paragraph [1]~any one of [4] and [8] It processes and obtains.

[10] manufacturing method of the polyethylene powder described in a kind of preceding paragraph [1] comprising：

The step of making vinyl polymerization in the presence of catalyst for olefines polymerizing and obtaining polyethylene powder,

The step of making catalyst for olefines polymerizing inactivate, and

The step of by polyethylene powder drying,

Wherein, in described the step of making catalyst for olefines polymerizing inactivate, to polyethylene powder spray body catalyst inactivation Agent.

[11] manufacturing method of the polyethylene powder as described in preceding paragraph [10], wherein

The catalyst deactivator is water, which is sprayed with vaporous.

[12] manufacturing method of the polyethylene powder as described in preceding paragraph [10] or [11], wherein

The catalyst deactivator is water, which is sprayed by vaporous and in the form of the mixed gas with inert gas Mist.

Invention effect

According to the present invention it is possible to realize that Continuous maching productivity is excellent, high-molecular-weight poly of product size excellent in stability Ethylene powder.

Description of the drawings

Fig. 1 is the infrared absorpting light spectra for indicating the aluminium hydroxide for being 50 μm or more by the minor axis that PE1 is obtained.

Fig. 2 is by the SEM-EDX distribution maps of the PE1 substances obtained with precipitated form.Understand many substances with high concentration Contain aluminium element.

Specific implementation mode

Hereinafter, mode for carrying out the present invention (hereinafter referred to as " present embodiment ") is described in detail.With Under present embodiment be for illustrate the present invention illustration, it is no intended to limit the invention to content below.The present invention It can suitably deform and implement in the range of its main idea.

[polyethylene powder]

The polyethylene powder of present embodiment, wherein the number for the aluminium hydroxide that minor axis is 50 μm or more is in polyethylene powder For 10 hereinafter, and viscosity average molecular weigh is 100000 or more in body 500g.

Polyethylene powder can be detached with aluminium hydroxide by the following method, can carry out the identification of aluminium hydroxide and Find out size, number.That is, the polyethylene powder of present embodiment is put into chloroform (proportion is 1.484 (20 DEG C)) and ethyl alcohol Mixed solvent (the volume ratio 3 of (proportion is 0.789 (20 DEG C))：1, be equivalent to proportion be 1.31) in, thus will be molten in the mixing The substance (mainly polyethylene powder) floated in agent is detached with sediment.

Specifically, first, ethyl alcohol 500mL is put into the glass system beaker of 3L, using with long 75mm, depth 22mm Teflon stirring blade mechanical agitator, be stirred at normal temperatures with 200rpm.Poly- second is slowly put into thereto Alkene powder 500g continues stirring 10 minutes after input.Then, 1500mL chloroforms are put into while agitating, are stirred for 10 minutes. Then, stop stirring, stand 0.5~2.0 hour, with the naked eye confirm to be mainly the floating of polyethylene powder.With 54 μm (280 of aperture Mesh) made of metal net lightly pick up the polyethylene powder of the floating and remove.Then, supernatant is abandoned by being decanted, after It is continuous to be lightly decanted until the solution residual quantity in beaker reaches about 50mL~about 100mL, supernatant is abandoned.Use about 10mL Remaining solution is quantitatively transferred in the glass system beaker of 200mL by chloroform, is stood again.It again will be molten by decantation gently Liquid measure is adjusted to about 50mL, and is transferred in separatory funnel.It is stood in separatory funnel again, by solvent portions (including sediment) Lower part solution about 10mL~about 20mL be stored in glass system screwed pipe.In order not to allow dust to use filter paper into the screwed pipe It covers, being arranged to diel in the ventilation equipment with exhaust equipment makes evaporation of the solvent.It is dried in vacuo at normal temperatures again.

Sediment can carry out member using SEM-EDX (scanning electron microscope-energy dispersion type x-ray analysis equipment) The identification of plain type.Thus, it is possible to confirm that sediment contains Al elements, but can also be observed other than Al elements Mg, The elements such as Ti, Cl, Si, Fe, Ni, Cr, Cu or C, H, O etc. from organic matter.In addition, passing through infrared absorption spectrum, member The analysis of plain analysis, thermogravimetric analysis, AL-NMR, XRD etc., can be analyzed and identified, can in particular with infrared absorption spectrum To confirm sediment as aluminium hydroxide.For example, using sediment as sample, (such as Dura Scope (ATR are used using ATR methods Crystallization plates：Diamond/ZnSe) etc.) infrared absorption spectrum can be obtained, by it, (three Tianjin and chemistry are public with commercially available aluminium hydroxide Take charge of the aluminium oxide etc. of manufacture) compare, it is possible thereby to be accredited as aluminium hydroxide.

The aluminium hydroxide that the minor axis of present embodiment is 50 μm or more, main component are aluminium hydroxide, but not only It is limited to this, other inorganic compounds or organic compound can also be contained.For example, it may be being attached with a small amount of polyethylene on surface Aluminium hydroxide etc..Even such substance, can also be detached with polyethylene powder by above-mentioned separation method.

About the size (minor axis) and its number of aluminium hydroxide, the confirmations such as above-mentioned SEM-EDX can be passed through.

The number for the aluminium hydroxide that minor axis is 50 μm or more, from Continuous maching productivity, the viewpoint of product size stability Consider, is 10 or less in 500g polyethylene powders.It is preferred that in 500g polyethylene powders be 8 hereinafter, more preferable 4 with Under, further preferred 3 hereinafter, still more preferably 2 hereinafter, further preferred 1 or less.

The number for the aluminium hydroxide that the size and minor axis of aluminium hydroxide are 50 μm or more can pass through tune as described later Section catalyst or the use level of co-catalyst, polymerizing condition, post-polymerization treatment condition control.

Here, being illustrated to " Continuous maching productivity " and " product size stability ".

For example, when processing is using secondary battery membrane as the microporous barrier of representative, it is using extruder etc., polyethylene powder is molten In solution to solvent and forming is film, but at this point, in order to remove insoluble matter etc., filter is arranged in the upstream side of die head Deng.At this point, when there is accumulation object in filter, the pressure of filter most nearby slowly rises, close to the torque pole of extruder The film thickness for the film for limiting or obtaining becomes uneven.Therefore, it is necessary to replace filter, needs to stop the operating of extruder, utilize Net exchanging device etc. replaces filter, thus influences the continuous production of product processing, and product yield reduces.

On the other hand, when spinning is processed using high strength fibre as the silk of representative, using extruder etc., by polyethylene powder It is silk to be dissolved into solvent and form, but at this point, in order to remove insoluble matter etc., filter is arranged in the upstream side of die head Deng.At this point, when there is accumulation object in filter, the pressure of filter most nearby slowly rises, close to the torque pole of extruder The silk for the silk for limiting or obtaining directly becomes uneven or generates fracture of wire.Therefore, it is necessary to replace filter, need to stop squeezing out The operating of machine replaces filter using net exchanging device etc., thus influences the continuous production of product processing, and product yield reduces.

In the present invention, " Continuous maching productivity " for example to process microporous barrier or high strength fibre when filter most nearby Pressure, which rises, to be indicated, the pressure by filter most nearby rise slowly or be barely perceivable pressure rising regard as it is continuous Processing throughput is excellent.In addition, " product size stability " indicates microporous barrier with the stability of film thickness, for high strength fiber Dimension is indicated with the stability of string diameter, and the deviation of these indexs is regarded as product size excellent in stability less.

The aluminium hydroxide that minor axis is 50 μm or more is 10 in 500g polyethylene powders hereinafter, unexpectedly to continuous Processing throughput and product size stability make a significant impact.That is, using the polyethylene powder of present embodiment as raw material When, the filter (or the frequency replaced is small) of extruder, and obtained film in the case of microporous barrier need not be replaced Thick extremely stable, obtained string diameter is extremely stable in the case of fiber or silk.

On the other hand, sometimes with using calcium stearate, zinc stearate as the aliphatic carboxylic acid of representative in polyethylene powder Metal salt etc..Although such substance different from aluminium hydroxide is aluminium hydroxide but substance of the minor axis less than 50 μm Whether there is or not have no significant effect above-mentioned characteristic.The hydrogen for being 50 μm or more only by the minor axis that will contain in polyethylene powder The number of aluminium oxide is adjusted to 10 hereinafter, these effects can be showed, this is unexpected.

As described above, the polyethylene powder of present embodiment, the aluminium hydroxide that wherein minor axis is 50 μm or more is that regulation contains Therefore amount is hereinafter, be that Continuous maching productivity is excellent, polyethylene powder of product size excellent in stability.On the other hand, this reality The polyethylene powder of mode is applied, even if being less than 50 μm of aluminium hydroxide containing minor axis, Continuous maching productivity and product size are steady It is qualitative terrifically to deteriorate, from the viewpoint of acid resistance, preferably comprise the aluminium hydroxide that minor axis is less than 50 μm.

The polyethylene powder of present embodiment preferably comprises aluminium element.Aluminium element content in polyethylene powder is from acid resistance From the viewpoint of preferably 0.2ppm or more, more preferably 1ppm or more, further preferably 2ppm or more.About polyethylene powder The upper limit value of aluminium element content in body, is not particularly limited, and considers from viewpoints such as the resistance to long term deterioration characteristics of fiber, preferably 100ppm, more preferable 50ppm, further preferred 20ppm, particularly preferred 10ppm.

It, can be by carrying out ICP-MS to polyethylene powder about the aluminium element amount in the polyethylene powder of present embodiment (inductively coupled plasma mass spectrometry, detection limit 0.01ppm) is measured and is found out.

Aluminium element contained in polyethylene powder is mainly derived from aftermentioned catalyst or co-catalyst, by adjusting them Use level and polymerizing condition, aluminium element content contained in polyethylene powder can be controlled.

The polyethylene powder of present embodiment preferably comprises magnesium elements.Magnesium element content in polyethylene powder is broken from resistance to From the viewpoint of silk property, preferably 0.5ppm or more, and preferably 12ppm or less.Even more preferably 1.0ppm or more and 10ppm Below.Further especially more preferable 2.0ppm or more and 9ppm or less.The resistance to fracture of wire refers to making using polyethylene powder as raw material The not performance of fracture of wire when carrying out gel spinning processing with solvent.

It, can be by carrying out ICP- to polyethylene powder about the magnesium element content in the polyethylene powder of present embodiment MS (inductively coupled plasma mass spectrometry, detection limit 0.01ppm) is measured and is found out.

Magnesium element content contained in polyethylene powder is mainly derived from aftermentioned catalyst or co-catalyst, passes through adjusting Their use level and polymerizing condition, can control magnesium element content contained in polyethylene powder.

[polyethylene]

It as the polyethylene of present embodiment, is not particularly limited, includes specifically Alathon and ethylene and choosing The alpha-olefin of free carbon atom number 3~20, the cyclic olefin of carbon atom number 3~20, formula CH₂=CHR¹(here, R¹For carbon atom The aryl of number 6~20) in the group of compound and the straight chain of carbon atom number 4~20, branch or cricoid diene composition that indicates At least one alkene copolymer.As the alkene of copolymerization, from using film and fiber as the heat resistance of the formed body of representative, intensity From the viewpoint of, preferably propylene and 1- butylene.Ethylene molar ratio shared in polyethylene be typically preferred to 50% or more and 100% hereinafter, more preferable 80% or more and 100% hereinafter, further preferred 90% or more and 100% or less.

The viscosity average molecular weigh (Mv) of the polyethylene of present embodiment is 100000 or more.The polyethylene of present embodiment glues Average molecular weight (Mv) can be dense by the ratio found out at 135 DEG C by the way that polyethylene to be dissolved into different concentration in decahydronaphthalenes Viscosity is extrapolated to concentration 0 and finds out limiting viscosity [η] (dL/g), is calculated using mathematical expression A below by the limiting viscosity.

Mv=(5.34 × 10⁴)×[η]^1.49... mathematical expression A

Here, viscosity average molecular weigh is 100000 or more, secondary battery membrane is suitble to use.In particular, as lithium ion secondary Battery diaphragm is used, and from the viewpoint of productivity, draftability and film-strength, preferably 100000 or more and 2000000 hereinafter, more excellent It selects 150000 or more and 1500000 hereinafter, further preferred 200000 or more and 1200000 or less.

In addition, viscosity average molecular weigh is 4000000 or more, especially lead accumulator diaphragm is suitable as in secondary battery membrane With.It is used as lead accumulator diaphragm, from the viewpoint of acid resistance characteristic, more preferable 5000000 or more, it is especially further excellent Select 6000000 or more.At this point, the upper limit of viscosity average molecular weigh is not particularly limited, from the viewpoint of industrial productivity, preferably 10000000, more preferable 8000000.

In addition, viscosity average molecular weigh is 1500000 or more, it is suitble to high strength fiber Wesy.As high strength fiber Wesy, especially From the viewpoint of stretch process, high intensity, the long-time quality of fiber, more preferable 2000000 or more, further preferably 3000000 or more, particularly preferred 4000000 or more.At this point, the upper limit of viscosity average molecular weigh is not particularly limited, from industrial production From the viewpoint of rate, preferably 10000000, more preferable 8000000.

[polymerization of polyethylene]

The polyethylene of present embodiment by the presence of catalyst for olefines polymerizing by ethylene (or ethylene and ethylene Alkene in addition) polymerization obtain.

The catalyst component used in the manufacture of the polyethylene of present embodiment, is not particularly limited, and can use general Ziegler-Natta catalyst or metallocene catalyst manufacture.

As Ziegler-Natta catalyst, solid catalyst component [A] and organo-metallic compound ingredient are preferably comprised The organo-magnesium compound (A-1) for dissolving in unreactive hydrocarbons solvent that [B], wherein solid catalyst component [A] are indicated by formula 1 with The titanium compound (A-2) that formula 2 indicates reacts and the catalyst for olefines polymerizing of manufacture.

(A-1)：(M¹)_α(Mg)_β(R²)_a(R³)_bY¹ _cFormula 1

(in formula, M¹To belong to the metallic atom for the group being made of the 12nd race of the periodic table of elements, the 13rd race and the 14th race, R²With R³For 2 or more and 20 alkyl below of carbon atom number, Y¹For alkoxy, siloxy, allyloxy, amino, amide groups ,-N=C- R⁴,R⁵、-SR⁶(wherein, R⁴、R⁵And R⁶Indicate 1 or more and 20 alkyl below of carbon atom number.When c is 2, Y¹Respectively may not be used Together.), any one in beta-keto acid residue, α, β, a, b and c are the real number for meeting following relationship.0≤α, 0 ＜ β, 0≤a, 0≤ B, (wherein, n indicates M by 0≤c, 0 ＜ a+b, 0≤c/ (alpha+beta)≤2 ,+2 β of n α=a+b+c¹Valence.))

(A-2)：Ti(OR⁷)_dX¹ _(4-d)Formula 2

(in formula, d is 0 or more and 4 real numbers below, R⁷For 1 or more and 20 alkyl below of carbon atom number, X¹For halogen original Son.)

In addition, as unreactive hydrocarbons solvent in use in the reacting of (A-1) and (A-2), it is not particularly limited, it specifically can be with Enumerate the aliphatic hydrocarbons such as pentane, hexane, heptane；The aromatic hydrocarbon such as benzene, toluene；And alicyclic such as hexamethylene, hexahydrotoluene etc..

First, (A-1) is illustrated.(A-1) to be indicated in the form of the organic magnesium complex for dissolving in unreactive hydrocarbons solvent, But include the complex compound of whole dialkyl magnesium compounds and the compound and other metallic compounds.Symbol α, β, a, b The stoichiometry of the valence and substituent group of metallic atom is indicated with+2 β of relational expression n α=a+b+c of c.

In formula 1, by R²And R³2 or more and 20 alkyl below of carbon atom number of expression, is not particularly limited, in particular Alkyl, naphthenic base or aryl can enumerate such as ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, cyclohexyl, phenyl Deng.Wherein, optimizing alkyl.α>In the case of 0, as metallic atom M¹, can use belong to by the 12nd race of the periodic table of elements, The metallic atom of the group of 13 races and the 14th race composition, can enumerate such as zinc, boron, aluminium.Wherein, preferably aluminium, zinc.

Magnesium is relative to metallic atom M¹The ratio between beta/alpha be not particularly limited, preferably 0.1 or more and 30 hereinafter, more preferably 0.5 or more and 10 or less.In addition, using α=0 defined organo-magnesium compound when, such as R²For 1- methyl-propyls etc. whens, can It is dissolved in unreactive hydrocarbons solvent, such compound also can provide preferred result to present embodiment.In formula 1, R when α=0²、 R³Preferably satisfy any one group in group as shown below (1), group (2), (3) three groups of group.

Group (1)：R²、R³It is at least one be 4 or more and 6 secondary alkyl below of carbon atom number or tertiary alkyl, preferably R²、R³ It is 4 or more and 6 alkyl below of carbon atom number, at least one for secondary alkyl or tertiary alkyl.

Group (2)：R²And R³For the mutually different alkyl of carbon atom number, preferably R²Alkyl, R for carbon atom number 2 or 3³For carbon The alkyl of 4 or more atomicity.

Group (3)：R²、R³At least one alkyl for 6 or more carbon atom number, preferably R²、R³Contained in carbon atom number it With the alkyl for 12 or more.

These groups are enumerated in detail below.As in group (1) 4 or more and 6 secondary alkyl below of carbon atom number or uncle Alkyl can specifically enumerate 1- methyl-propyls, 2- methyl-propyls, 1,1- dimethyl ethyls, 2- methyl butyls, 2- ethyls third Base, 2,2- dimethyl propyls, 2- methyl amyls, 2- ethyl-butyls, 2,2- dimethylbutyls, 2- methyl -2- ethyl propyls etc..Its In, particularly preferred 1- methyl-propyls.

Secondly, as the alkyl of the carbon atom number 2 or 3 in group (2), ethyl, 1- Methylethyls, third can specifically be enumerated Base etc..Wherein particularly preferred ethyl.In addition, the alkyl as 4 or more carbon atom number, is not particularly limited, can specifically arrange Lift butyl, amyl, hexyl, heptyl, octyl etc..Wherein, particularly preferred butyl, hexyl.

In addition, the alkyl as 6 or more carbon atom number in group (3), is not particularly limited, can specifically enumerate oneself Base, heptyl, octyl, nonyl, decyl, phenyl, 2- naphthalenes etc..Optimizing alkyl in alkyl, particularly preferably hexyl, octyl in alkyl.

In general, when carbon atom number contained in alkyl increases, there is the tendency being easy to be dissolved in unreactive hydrocarbons solvent, The tendency that also viscosity with solution increases.Therefore, operationally consider the alkyl, it is preferable to use the long-chain of appropriateness.On in addition, State after organo-magnesium compound can be diluted with unreactive hydrocarbons solvent and use, though contain in the solution or the ether of residual minim, ester, The lewis base properties such as amine compound can also allow to use.

Secondly, to Y¹It illustrates.In formula 1, Y¹For alkoxy, siloxy, allyloxy, amino, amide groups ,-N=C- R⁴,R⁵、-SR⁶(here, R⁴、R⁵And R⁶Each independently represent 2 or more and 20 alkyl below of carbon atom number), beta-keto acid residue In any one.

As R in formula 1⁴、R⁵And R⁶The alkyl of expression, preferably 1 or more and 12 alkyl or aryl below of carbon atom number, it is special Not preferred 3 or more and 10 alkyl or aryl below of carbon atom number.Be not particularly limited, can specifically enumerate such as methyl, Ethyl, propyl, 1- Methylethyls, butyl, 1- methyl-propyls, 1,1- dimethyl ethyls, amyl, hexyl, 2- methyl amyls, 2- second Base butyl, 2- ethylpentyls, 2- ethylhexyls, 2- ethyl -4- methyl amyls, 2- propylheptyls, 2- ethyl -5- Methyl Octyls, Octyl, nonyl, decyl, phenyl, naphthalene etc..Wherein, particularly preferred butyl, 1- methyl-propyls, 2- methyl amyls and 2- ethyl hexyls Base.

In addition, in formula 1, Y¹Preferably alkoxy or siloxy.It as alkoxy, is not particularly limited, specifically preferably For methoxyl group, ethyoxyl, propoxyl group, 1- methyl ethoxies, butoxy, 1- methyl propoxyl group, 1,1- dimethylethyloxies, penta oxygen Base, hexyloxy, 2- methyl amoxy, 2- ethyl-butoxies, 2- ethyls amoxy, 2- ethyl hexyl oxies, 2- ethyl -4- methylpents Oxygroup, 2- propyl oxygroup in heptan, 2- ethyl -5- methyl octyloxy, octyloxy, phenoxy group, naphthoxy.Wherein, more preferable butoxy, 1- methyl propoxyl group, 2- methyl amoxy and 2- ethyl hexyl oxies.It as siloxy, is not particularly limited, specifically preferred hydrogen Dimethylsilyl bis, ethyl hydrogen methyl siloxy, diethyl hydrogen siloxy, trimethylsiloxy group, ethyl dimethylsilyl bis, two Ethyl-methyl siloxy, triethyl group siloxy etc..Wherein, more preferable hydrogen dimethylamino base siloxy, ethyl hydrogen methyl siloxy, diethyl Base hydrogen siloxy, trimethylsiloxy group.

The synthetic method of (A-1) is not particularly limited in present embodiment, can be by making to belong to by formula R²MgX¹And formula R² ₂Mg(R²Meaning it is the same, X¹For halogen) composition group organo-magnesium compound and belong to by formula M¹R³ _nAnd M¹R³ _(n-1)H(M¹With R³Meaning it is the same, n indicate M¹Valence) composition group organo-metallic compound in unreactive hydrocarbons solvent at 25 DEG C or more And 150 DEG C or less reactions, then formula Y as needed¹-H(Y¹Meaning it is the same) indicate compound reaction or make with Y¹ The organo-magnesium compound and/or organo-aluminum compound of the functional group of expression react to synthesize.Wherein, make to dissolve in unreactive hydrocarbons solvent Organo-magnesium compound and formula Y¹When the compound reaction that-H is indicated, the sequence of reaction is not particularly limited, can be used The adding type Y in organic metal magnesium compound¹- H indicate compound method, in formula Y¹It is added in the compound that-H is indicated Any one method in the method for machine magnesium compound or the method for adding the two simultaneously.

In present embodiment, Y in (A-1)¹Ranging from 0 of molar composition ratio c/ (alpha+beta) relative to whole metallic atoms ≤ c/ (alpha+beta)≤2, preferably 0≤c/ (alpha+beta)<1.Pass through Y¹Relative to whole metallic atoms molar composition ratio be 2 hereinafter, With raising (A-1) to the reactive tendency of (A-2).

Hereinafter, being illustrated to (A-2).(A-2) it is the titanium compound indicated by formula 2.

(A-2)：Ti(OR⁷)_dX¹ _(4-d)Formula 2

(in formula, d is 0 or more and 4 real numbers below, R⁷For 1 or more and 20 alkyl below of carbon atom number, X¹For halogen original Son)

In equation 2 above, d is preferably 0 or more and 1 hereinafter, further preferably d is 0.In addition, in formula 2, as R⁷The hydrocarbon of expression Base is not particularly limited, can specifically enumerate methyl, ethyl, propyl, butyl, amyl, hexyl, 2- ethylhexyls, heptyl, The aliphatic groups such as octyl, decyl, allyl；The alicyclic hydrocarbon radicals such as cyclohexyl, 2- methylcyclohexyls, cyclopenta；The virtues such as phenyl, naphthalene Fragrant alkyl etc..Wherein, preferred fat alkyl.As X¹The halogen of expression can enumerate chlorine, bromine, iodine.Wherein, preferred chlorine.This reality It applies in mode, (A-2) is most preferably titanium tetrachloride.In present embodiment, it can be mixed two or more selected from above-mentioned compound It closes and uses.

Hereinafter, being illustrated with reacting for (A-2) to (A-1).The reaction carries out preferably in unreactive hydrocarbons solvent, further It is preferred that being carried out in the aliphatic solvents such as hexane, heptane.It is not special for the molar ratio of (A-1) and (A-2) in the reaction Limitation, Ti atoms contained in (A-2) are preferably 0.1 or more relative to the molar ratio (Ti/Mg) of Mg atoms contained in (A-1) And 10 hereinafter, more preferably 0.3 or more and 3 or less.Reaction temperature is not particularly limited, preferably at -80 DEG C or more and 150 DEG C or less range in carry out, more preferably carried out in the range of -40 DEG C~100 DEG C.(A-1) do not have with the order of addition of (A-2) Have special limitation, can be add after (A-1) (A-2), add after (A-2) (A-1), by (A-1) and (A-2) simultaneously Any one method of addition, preferably by (A-1) and (A-2) while the method for addition.In present embodiment, pass through above-mentioned reaction Obtained solid catalyst component [A] is used in the form of the pulp solution for using unreactive hydrocarbons solvent.

As other examples of the Ziegler-Natta catalyst used in present embodiment, solid catalyst is preferably comprised Ingredient [C] and organo-metallic compound ingredient [B], solid catalyst component [C] dissolve in unreactive hydrocarbons by what is indicated in formula 3 The organo-magnesium compound (C-1) of solvent is reacted with the chlorinating agent (C-2) that formula 4 indicates and 5 table of load type on the carrier (C-3) for preparing Titanium compound (C-5) that the organo-magnesium compound (C-4) for dissolving in unreactive hydrocarbons solvent and formula 6 that show indicate and the alkene that manufactures is poly- Catalysts.

(C-1)：(M²)_γ(Mg)_δ(R⁸)_e(R⁹)_f(OR¹⁰)_gFormula 3

(in formula, M²To belong to the metallic atom for the group being made of the 12nd race of the periodic table of elements, the 13rd race and the 14th race, R⁸、 R⁹And R¹⁰Respectively 2 or more and 20 alkyl below of carbon atom number, γ, δ, e, f and g are the real number for meeting following relationship.0≤ γ、0<δ、0≤e、0≤f、0≤g、0<E+f, 0≤g/ (γ+δ)≤2 ,+2 δ of k γ=e+f+g are (here, k indicates M²Atom Valence.))

(C-2)：H_hSiCl_iR¹¹ _(4-(h+i))Formula 4

(in formula, R¹¹For 1 or more and 12 alkyl below of carbon atom number, h and i are the real number for meeting following relationship.0<h、0< i、0<h+i≦4)

(C-4)：(M¹)_α(Mg)_β(R²)_a(R³)_bY¹ _cFormula 5

(in formula, M¹To belong to the metallic atom for the group being made of the 12nd race of the periodic table of elements, the 13rd race and the 14th race, R²With R³For 2 or more and 20 alkyl below of carbon atom number, Y¹For alkoxy, siloxy, allyloxy, amino, amide groups ,-N=C- R⁴,R⁵、-SR⁶(here, R⁴、R⁵And R⁶Indicate 1 or more and 20 alkyl below of carbon atom number.When c is 2, Y¹Respectively may not be used Together.), any one in beta-keto acid residue, α, β, a, b and c are the real number for meeting following relationship.0≤α、0<β、0≤a、0≤ b、0≤c、0<(alpha+beta)≤2 ,+2 β of n α=a+b+c are (here, n indicates M by a+g, 0≤c/¹Valence.))

(C-5)：Ti(OR⁷)_dX¹ _(4-d)Formula 6

First, (C-1) is illustrated.(C-1) to be indicated in the form of the organic magnesium complex for dissolving in unreactive hydrocarbons solvent, But include the complex compound of whole dialkyl magnesium compounds and the compound and other metallic compounds.The symbol γ of formula 3, + 2 δ of relational expression k γ of δ, e, f and g=e+f+g indicate the stoichiometry of the valence and substituent group of metallic atom.

In above formula, by R⁸Or R⁹The alkyl of expression, is not particularly limited, specifically respectively alkyl, naphthenic base or aryl, It can enumerate such as methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, cyclohexyl, phenyl.Wherein, preferably R⁸ And R⁹Respectively alkyl.α>In the case of 0, as metallic atom M², can use belong to by the 12nd race of the periodic table of elements, the 13rd The metallic atom of the group of race and the 14th race composition, can enumerate such as zinc, boron, aluminium.Wherein, particularly preferred aluminium, zinc.

Magnesium is relative to metallic atom M²The ratio between δ/γ be not particularly limited, preferably 0.1 or more and 30 hereinafter, more preferably 0.5 or more and 10 or less.In addition, using γ=0 defined organo-magnesium compound when, such as R⁸For 1- methyl-propyls etc. whens, Unreactive hydrocarbons solvent is dissolved in, such compound also can provide preferred result to present embodiment.In formula 3, when γ=0 R⁸、R⁹Any one group in group (1) preferably as shown below, group (2), (3) three groups of group.

Group (1)：R⁸、R⁹It is at least one be 4 or more and 6 secondary alkyl below of carbon atom number or tertiary alkyl, preferably R⁸、R⁹ It is 4 or more and 6 alkyl below of carbon atom number, at least one for secondary alkyl or tertiary alkyl.

Group (2)：R⁸And R⁹For the mutually different alkyl of carbon atom number, preferably R⁸Alkyl, R for carbon atom number 2 or 3⁹For carbon The alkyl of 4 or more atomicity.

Group (3)：R⁸、R⁹At least one alkyl for 6 or more carbon atom number, preferably R⁸、R⁹Contained in carbon atom number it With the alkyl for 12 or more.

These groups are enumerated in detail below.As in group (1) 4 or more and 6 secondary alkyl below of carbon atom number or uncle Alkyl can specifically use 1- methyl-propyls, 2- methyl-propyls, 1,1- dimethyl ethyls, 2- methyl butyls, 2- ethyls third Base, 2,2- dimethyl propyls, 2- methyl amyls, 2- ethyl-butyls, 2,2- dimethylbutyls, 2- methyl -2- ethyl propyls etc..Its In, particularly preferred 1- methyl-propyls.

Secondly, as the alkyl of the carbon atom number 2 or 3 in group (2), ethyl, 1- Methylethyls, propyl etc. can be enumerated. Wherein particularly preferred ethyl.In addition, the alkyl as 4 or more carbon atom number, is not particularly limited, fourth can be specifically enumerated Base, amyl, hexyl, heptyl, octyl etc..Wherein, particularly preferred butyl, hexyl.

In general, when carbon atom number contained in alkyl increases, there is the tendency being easy to be dissolved in unreactive hydrocarbons solvent, And the tendency that the viscosity with solution increases.Therefore, operationally consider the alkyl, it is preferable to use the long-chain of appropriateness.In addition, Above-mentioned organo-magnesium compound is used in the form of unreactive hydrocarbons solution, even if containing in the solution or the ether of residual minim, ester, amine Equal lewis base properties compound can also allow to use.

Secondly, to alkoxy (OR¹⁰) illustrate.As R¹⁰The alkyl of expression, preferably carbon atom number 1 or more and 12 with Under alkyl or aryl, 3 or more and 10 alkyl or aryl below of particularly preferred carbon atom number.As R¹⁰, it is not particularly limited, Can specifically enumerate methyl, ethyl, propyl, 1- Methylethyls, butyl, 1- methyl-propyls, 1,1- dimethyl ethyls, amyl, Hexyl, 2- methyl amyls, 2- ethyl-butyls, 2- ethylpentyls, 2- ethylhexyls, 2- ethyl -4- methyl amyls, 2- propyl heptan Base, 2- ethyl -5- Methyl Octyls, octyl, nonyl, decyl, phenyl, naphthalene etc..Wherein, particularly preferred butyl, 1- methyl-propyls, 2- methyl amyls and 2- ethylhexyls.

In present embodiment, the synthetic method of (C-1) is not particularly limited, and preferably makes to belong to by formula R⁸MgX¹And formula R⁸ ₂Mg(R⁸Meaning it is the same, X¹For halogen atom) composition group organo-magnesium compound and belong to by formula M²R⁹ _kAnd formula M⁷R⁹ _(k-1) H(M²、R⁹It is the same with the meaning of k) composition group organo-metallic compound in unreactive hydrocarbons solvent 25 DEG C or more and 150 DEG C with Under temperature under react, as needed then with R⁹(R⁹Meaning it is the same) indicate alkyl alcohol or dissolve in inertia Hydrocarbon solvent has R⁹The method of alkoxyl magnesium compound and/or the alkoxy aluminum compound reaction of the alkyl of expression.

Wherein, when the organo-magnesium compound for dissolving in unreactive hydrocarbons solvent being made to be reacted with alcohol, for the no spy of the sequence of reaction Do not limit, can use in organo-magnesium compound add alcohol method, in alcohol add organo-magnesium compound method or Any one method in the method that the two is added simultaneously.In present embodiment, about dissolving in the organic of unreactive hydrocarbons solvent The reactive ratio of magnesium compound and alcohol is not particularly limited, reaction the result is that in obtained organo-magnesium compound containing alkoxy Alkoxy relative to whole metallic atoms molar composition ratio g/ (γ+δ) be 0≤g/ (γ+δ)≤2, preferably 0≤g/ (γ+ δ)<1。

Hereinafter, being illustrated to (C-2).(C-2) it is the expression of formula 4, the silicon chloride chemical combination at least one Si -- H bond Object.

(C-2)：H_hSiCl_iR¹¹ _(4-(h+i))Formula 4

In formula 4, R¹¹The alkyl of expression is not particularly limited, in particular aliphatic group, alicyclic hydrocarbon radical, aryl radical, can To enumerate such as methyl, ethyl, propyl, 1- Methylethyls, butyl, amyl, hexyl, octyl, decyl, cyclohexyl, phenyl.Its In, preferred 1 or more and 10 alkyl below of carbon atom number, the carbon atom numbers 1 such as more preferable methyl, ethyl, propyl, 1- Methylethyls ~3 alkyl.In addition, h and i is the number for being more than 0 for the relationship for meeting h+i≤4, preferably i is 2 or more and 3 or less.

It as these compounds, is not particularly limited, can specifically enumerate：HSiCl₃、HSiCl₂CH₃、HSiCl₂C₂H₅、 HSiCl₂(C₃H₇)、HSiCl₂(2-C₃H₇)、HSiCl₂(C₄H₉)、HSiCl₂(C₆H₅)、HSiCl₂(4-Cl-C₆H₄)、HSiCl₂(CH =CH₂)、HSiCl₂(CH₂C₆H₅)、HSiCl₂(1-C₁₀H₇)、HSiCl₂(CH₂CH=CH₂)、H₂SiCl(CH₃)、H₂SiCl(C₂H₅)、 HSiCl(CH₃)₂、HSiCl(C₂H₅)₂、HSiCl(CH₃)(2-C₃H₇)、HSiCl(CH₃)(C₆H₅)、HSiCl(C₆H₅)₂Deng.It can make With the silicon chloride compound of the two or more mixtures comprising these compounds or selected from these compounds.Wherein, preferably HSiCl₃、HSiCl₂CH₃、HSiCl(CH₃)₂、HSiCl₂(C₃H₇), more preferable HSiCl₃、HSiCl₂CH₃。

Hereinafter, being illustrated with reacting for (C-2) to (C-1).It is preferably in advance that (C-2) is molten using unreactive hydrocarbons when reaction The chlorohydrocarbons such as agent, 1,2- dichloroethanes, o-dichlorohenzene, dichloromethane；The ethers medium such as ether, tetrahydrofuran；Or they It is used after blending agent dilution.Wherein, consider from the aspect of performance of catalyst, more preferable unreactive hydrocarbons solvent.(C-1) with (C-2) Reactive ratio be not particularly limited, silicon atom contained in (C-2) relative to 1 mole of magnesium atom contained in (C-1) preferably For 0.01 mole or more and 100 moles hereinafter, more preferable 0.1 mole or more and 10 moles or less.

The reaction method of (C-1) and (C-2) are not particularly limited, can use and import (C-1) and (C-2) simultaneously Reactor and adding method while reacted, will (C-2) in advance after input reactor will (C-1) importing reactor side Method or by (C-1) in advance input reactor after will (C-2) importing reactor method in any one method.Wherein, excellent The method that (C-1) will be imported reactor by choosing after (C-2) in advance input reactor.By above-mentioned carrier (C-3) obtained by the reaction, It is preferred that after being detached by filtering or decantation, fully washed using unreactive hydrocarbons solvent to remove unreacted reactant or by-product Deng.

The reaction temperature of (C-1) and (C-2) are not particularly limited, preferably 25 DEG C or more and 150 DEG C hereinafter, more preferably 30 DEG C or more and 120 DEG C hereinafter, further preferred 40 DEG C or more and 100 DEG C or less.By (C-1) and (C-2) while importing anti- While answering device and reacted in adding method, preferably the temperature of reactor is adjusted to set point of temperature in advance, is carried out same The temperature in reactor is adjusted to set point of temperature while Shi Tianjia, thus adjusts reaction temperature to set point of temperature.By (C- 2) (C-1) is imported in the method for reactor after input reactor in advance, input is preferably had to the reaction of the silicon chloride compound The temperature of device is adjusted to set point of temperature, is arrived the temperature adjusting in reactor while which is imported reactor Thus set point of temperature is adjusted reaction temperature to set point of temperature.It is reacted (C-2) is imported after (C-1) in advance input reactor In the method for device, preferably input there is the temperature of the reactor of (C-1) adjust to set point of temperature, (C-2) is imported into reactor The temperature in reactor is adjusted to set point of temperature simultaneously, thus adjusts reaction temperature to set point of temperature.

Hereinafter, being illustrated to organo-magnesium compound (C-4).As (C-4), preferably indicated by formula 5 (C-4) above-mentioned.

(C-4)：(M¹)_α(Mg)_β(R²)_a(R³)_bY¹ _cFormula 5

(in formula, M¹To belong to the metallic atom for the group being made of the 12nd race of the periodic table of elements, the 13rd race and the 14th race, R²With R³For 2 or more and 20 alkyl below of carbon atom number, Y¹For alkoxy, siloxy, allyloxy, amino, amide groups ,-N=C- R⁴,R⁵、-SR⁶(here, R⁴、R⁵And R⁶Indicate 1 or more and 20 alkyl below of carbon atom number.When c is 2, Y¹Respectively may not be used Together.), any one in beta-keto acid residue, α, β, a, b and c are the real number for meeting following relationship.0≤α, 0 ＜ β, 0≤a, 0≤ B, 0≤c, 0 ＜ a+b, 0≤c/ (alpha+beta)≤2 ,+2 β of n α=a+b+c are (here, n indicates M¹Valence.))

About the usage amount of (C-4), mole of the magnesium atom relative to titanium atom contained in (C-5) contained in (C-4) Than being preferably 0.1 or more and 10 hereinafter, more preferably 0.5 or more and 5 or less.

The reaction temperature of (C-4) and (C-5) are not particularly limited, preferably -80 DEG C or more and 150 DEG C hereinafter, more excellent - 40 DEG C of choosing or more and 100 DEG C of ranges below.

For (C-4) use when concentration be not particularly limited, be preferably in terms of titanium atom contained in (C-4) 0.1mol/L or more and 2mol/L are hereinafter, more preferably 0.5mol/L or more and 1.5mol/L or less.In addition, the dilution of (C-4) In it is preferable to use unreactive hydrocarbons solvents.

On (C-3) add (C-4) and (C-5) sequence be not particularly limited, can be (C-4) afterwards addition (C-5), (C-5) afterwards add (C-4), will (C-4) and (C-5) and meanwhile add any one method.Wherein, preferably by (C-4) and (C- 5) at the same addition method.(C-4) and the reaction of (C-5) is carried out in unreactive hydrocarbons solvent, it is preferable to use the fat such as hexane, heptane Hydrocarbon solvent.The catalyst obtained in this way is used in the form of the pulp solution for using unreactive hydrocarbons solvent.

Hereinafter, being illustrated to (C-5).In present embodiment, (C-5) is the titanium compound that formula 6 above-mentioned indicates.

(C-5)：Ti(OR⁷)_dX¹ _(4-d)Formula 6

As R in formula 6⁷The alkyl of expression, is not particularly limited, can specifically enumerate methyl, ethyl, propyl, butyl, The aliphatic groups such as amyl, hexyl, 2- ethylhexyls, heptyl, octyl, decyl, allyl；Cyclohexyl, 2- methylcyclohexyls, ring penta The alicyclic hydrocarbon radicals such as base；Aryl radicals such as phenyl, naphthalene etc..Wherein, preferred fat alkyl.As X¹The halogen of expression, without spy It does not limit, can specifically enumerate chlorine, bromine, iodine.Wherein, preferred chlorine.It a kind of can be used alone selected from above-mentioned (C-5), Two or more may be used in combination.

It as the usage amount of (C-5), is not particularly limited, the molar ratio relative to magnesium atom contained in carrier (C-3) It is preferred that 0.01 or more and 20 hereinafter, particularly preferred 0.05 or more and 10 or less.

It for the reaction temperature of (C-5), is not particularly limited, preferably -80 DEG C or more and 150 DEG C hereinafter, more preferably -40 DEG C Above and 100 DEG C of ranges below.

In present embodiment, on (C-3) load (C-5) method be not particularly limited, can use make relatively The method reacted in (C-3) excessive (C-5), the method that (C-5) is effectively loaded by using third ingredient, preferably Pass through the method for (C-5) and organo-magnesium compound (C-4) loaded by reaction.

Hereinafter, being illustrated to the organo-metallic compound ingredient [B] in present embodiment.The solid of present embodiment is urged Agent ingredient is by being composed the catalyst for polymerization for high activity with organo-metallic compound ingredient [B].Organometallic Polymer component [B] is otherwise referred to as " co-catalyst ".As organo-metallic compound ingredient [B], preferably contains and belong to by member The compound of the metal for the group that the 1st race of plain periodic table, the 2nd race, the 12nd race and the 13rd race form, particularly preferably organo-aluminium chemical combination Object and/or organo-magnesium compound.

As organo-aluminum compound, the compound of the expression of following formula 7 is preferably used alone or as a mixture.

AlR¹² _kZ¹ _(3-j)Formula 7

(in formula, R¹²For 1 or more and 20 alkyl below of carbon atom number, Z¹To belong to by hydrogen, halogen, alkoxy, allyl oxygen The group of the group of base, siloxy composition, j are 2 or more and 3 numbers below)

In equation 7 above, R¹²1 or more and 20 alkyl below of carbon atom number of expression is not particularly limited, and includes specifically fat Fat alkyl, aryl radical, alicyclic hydrocarbon radical, such as preferred trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, three (2- first Base propyl) aluminium (or triisobutyl aluminium), three amyl aluminium, three (3- methyl butyls) aluminium, three hexyl aluminium, trioctylaluminum, tridecyl aluminum Equal trialkylaluminiums；Diethyl aluminum chloride, ethylaluminum dichloride, bis- (2- methyl-propyls) aluminium chloride, ethyl aluminium sesquichloride, diethyl The aluminum halide compounds such as base aluminium bromide；The alkoxy aluminum compounds such as diethylaluminum ethoxide, bis- (2- methyl-propyls) butoxy aluminium； The silicon such as dimethyl hydrogen siloxy dimethyl aluminium, ethyl-methyl hydrogen siloxy diethyl aluminum, ethyl dimethylsilyl bis diethyl aluminum Oxygroup aluminium compound；And their mixture.Wherein, particularly preferred trialkyl aluminium compound.

As organo-magnesium compound, the organo-magnesium compound for dissolving in unreactive hydrocarbons solvent that preferably previously described formula 3 indicates.

(M²)_γ(Mg)_δ(R⁸)_e(R⁹)_f(OR¹⁰)_gFormula 3

The organo-magnesium compound includes whole to be indicated in the form of the organic magnesium complex for dissolving in unreactive hydrocarbons solvent Dialkyl magnesium compound and the compound and other metallic compounds complex compound.For γ, δ, e, f, g, M²、R⁸、R⁹、 OR¹⁰, as previously described, because dissolubility of the organo-magnesium compound preferably in unreactive hydrocarbons solvent is high, therefore preferably beta/alpha is 0.5 In the range of~10, in addition, more preferable M²For the compound of aluminium.

It is added to the polymerization system under polymerizing condition about by solid catalyst component and organo-metallic compound ingredient [B] Interior method, is not particularly limited, and the two can be respectively added in polymerization system, adds after the two can also be made to react in advance It is added in polymerization system.In addition, the ratio of the two of combination is not particularly limited, relative to solid catalyst component 1g, Organo-metallic compound ingredient [B] is preferably 1mmol or more and 3000mmol or less.

On the other hand, as the example for using metallocene catalyst, general transistion metal compound can be used.Example Such as, the manufacturing method described in Japan Patent 4868853 can be enumerated.Such metallocene catalyst is by a) having ring-type η The transistion metal compound of associativity anion ligand and can b) be reacted with the transistion metal compound and formed performance catalysis Both catalyst components of the activator of active complex compound are constituted.

The transistion metal compound with ring-type η associativity anion ligands used in present embodiment can be by for example Following formula 8 indicates.

L¹ _jW_kM³X² _pX³ _q... formula 8

In formula 8, L¹Each independently represent selected from by cyclopentadienyl group, indenyl, tetrahydro indenyl, fluorenyl, tetrahydrofluorenyl and η associativity ring-type anion ligands in the group of octahydrofluorenyl composition, the ligand according to circumstances have 1~8 substituent group, this takes It is former that Dai Ji is each independently alkyl, halogen atom, the halohydrocarbyl of carbon atom number 1~12, carbon selected from carbon atom number 1~20 The hydrocarbyl amino of subnumber 1~12, the oxyl of carbon atom number 1~12, the Dialkylamino of carbon atom number 1~12, carbon atom number 1 ~12 alkyl phosphino-, silicyl, amino silyl, the hydrocarbyloxysilyl group of carbon atom number 1~20 and halogenated first The group of silylation composition and the substituent group with 20 non-hydrogen atoms below.

In formula 8, M³Indicate the transition metal for belonging to the 4th race of the periodic table of elements for being+2 ,+3 or+4 selected from form oxidation number Group and at least one ligand L¹Carry out η⁵In conjunction with transition metal.

In formula 8, W indicates the divalent substituent with 50 or less non-hydrogen atoms, wherein respectively with the valence mumber of monovalence and L¹ And M³In conjunction with, thus with L¹And M³The divalent substituent of metallocycle, X is collectively formed²It each independently represents selected from by monovalence Anionic property σ mating types ligand and M³Divalent combine dianion σ mating types ligand and respectively with the valence of monovalence Number and L¹And M³In conjunction with the group that forms of dianion σ mating type ligands in, with 60 or less non-hydrogen atoms it is cloudy from Sub- property σ mating type ligands.

In formula 8, X²The coordinating compound of neutral Lewis base with 40 or less non-hydrogen atoms is each independently represented, X³Indicate the coordinating compound of neutral Lewis base.

J is 1 or 2, when wherein j is 2, according to circumstances two ligand Ls¹Pass through the bilvalent radical with 20 or less non-hydrogen atoms Group be combined with each other, the bivalent group be halogenated hydrocarbons diyl selected from hydrocarbon diyl, carbon atom number 1~12 by carbon atom number 1~20, The alkylene oxygroup of carbon atom number 1~12, the hydrocarbyleneamino of carbon atom number 1~12, silane diyl, halogenated silanes diyl and Asia Group in the group of first silicon substrate amino composition.

K is 0 or 1, p 0,1 or 2, wherein X²For the anionic property σ mating types ligand of monovalence or and L¹And M³In conjunction with When the anionic property σ mating type ligands of divalent, p is than M³Form oxidation number small 1 or more integer, in addition, X²For only with M³Knot When the anionic property σ mating type ligands of the divalent of conjunction, p is than M³Form oxidation number small (j+1) more than integer, q 0,1 or 2。

As the X ligand in the compound of above-mentioned formula 8²Example, can enumerate halide, carbon atom number 1~60 hydrocarbon Base, the oxyl of carbon atom number 1~60, the hydrocarbon amide groups of carbon atom number 1~60, carbon atom number 1~60 alkyl phosphide base, Alkyl sulfide base, silicyl, their the compound group etc. of carbon atom number 1~60.

As the coordinating compound X of neutral Lewis base in the compound of above-mentioned formula 8³Example, can enumerate phosphine, Ether, amine, the alkene of carbon atom number 2~40,40 diene below of carbon atom number, bivalent group etc. derived from these compounds.

In present embodiment, as the transistion metal compound with cyclic annular η associativities anion ligand, preferably previously described formula The transistion metal compound that 8 (wherein, j=1) are indicated.The preference of compound as previously described formula 8 (wherein, j=1) expression, The compound of the expression of following formula 9 can be enumerated.

In formula 9, M⁴Indicate in the group being made of titanium, zirconium and hafnium, the transition gold that form oxidation number is+2 ,+3 or+4 Belong to, R¹³It each independently represents selected from by hydrogen atom, the alkyl of carbon atom number 1~8, silicyl, germyl, cyano, halogen Substituent group in the group of plain atom and their compound group composition, with 20 or less non-hydrogen atoms, wherein the substitution Base R¹³For carbon atom number 1~8 alkyl, silicyl or germyl when, according to circumstances two adjacent substituent Rs¹³It can be with Be combined with each other and formed the group of divalent, thus with two adjacent substituent Rs¹³The cyclopentadienyl rings being respectively self-bonded Key between two carbon atoms forms ring together.

In formula 9, X⁴It each independently represents selected from by halide, the alkyl of carbon atom number 1~20, carbon atom number 1~18 Oxyl, the hydrocarbon amino of carbon atom number 1~18, silicyl, the hydrocarbon amide groups of carbon atom number 1~18, carbon atom number 1~18 Alkyl phosphide base, carbon atom number 1~18 alkyl sulfide base and they compound group composition group in, have The substituent group of 20 or less non-hydrogen atoms, wherein according to circumstances two substituent Xs⁴Carbon atom number 4~30 can be formed together The group of neutral conjugation diene or divalent.

In formula 9, Y²Expression-O- ,-S- ,-NR*- or-PR*-, wherein R* indicate hydrogen atom, carbon atom number 1~12 hydrocarbon The halogenated virtue of base, the oxyl of carbon atom number 1~8, silicyl, the halogenated alkyl of carbon atom number 1~8, carbon atom number 6~20 Base or their compound group.

In formula 9, Z²Indicate SiR*₂、CR*₂、SiR*₂SiR*₂、CR*₂CR*₂, CR*=CR*, CR*₂SiR*₂Or GeR*₂, In, R* is defined as above, n 1,2 or 3.

It, can be with as the transistion metal compound with ring-type η associativity anion ligands used in present embodiment Enumerate compound shown below.It as zirconyl compound, is not particularly limited, can specifically enumerate bis- (methyl rings penta 2 Alkenyl) zirconium dimethyl, bis- (n-butyl cyclopentadienyl) zirconium dimethyls, bis- (indenyl) zirconium dimethyls, bis- (1,3- diformazans basic rings penta Dialkylene) zirconium dimethyl, (pentamethylcyclopentadiene base) (cyclopentadienyl group) zirconium dimethyl, bis- (cyclopentadienyl group) dimethyl Zirconium, bis- (pentamethylcyclopentadiene base) zirconium dimethyls, bis- (fluorenyl) zirconium dimethyls, ethylenebis (indenyl) zirconium dimethyl, sub- second Bis- (4,5,6,7- tetrahydrochysene -1- indenyls) zirconium dimethyls of base, ethylenebis (4- methyl-1s-indenyl) zirconium dimethyl, ethylenebis (5- Methyl-1-indenyl) zirconium dimethyl, ethylenebis (6- methyl-1s-indenyl) zirconium dimethyl, ethylenebis (7- methyl-1s-indenyl) Zirconium dimethyl, ethylenebis (5- methoxyl group -1- indenyls) zirconium dimethyl, ethylenebis (2,3- dimethyl -1- indenyls) dimethyl Zirconium, ethylenebis (4,7- dimethyl -1- indenyls) zirconium dimethyl, ethylenebis (4,7- dimethoxy -1- indenyls) zirconium dimethyl, Di-2-ethylhexylphosphine oxide (cyclopentadienyl group) zirconium dimethyl, isopropylidene (cyclopentadienyl group) zirconium dimethyl, isopropylidene (cyclopentadiene Base-fluorenyl) zirconium dimethyl, bis- (cyclopentadienyl group) zirconium dimethyls of silicylene, dimethylated methylene silylation (cyclopentadiene Base) zirconium dimethyl etc..

It as ti-based compound, is not particularly limited, can specifically enumerate：[(N- tert-butylamides base) (tetramethyl- η⁵Cyclopentadienyl group) -1,2- ethane diyl] dimethyl titanium, [(N- tert-butylamides base) (tetramethyl-η⁵Cyclopentadienyl group) two Methyl-monosilane] dimethyl titanium, [(N- methyl acylaminos) (tetramethyl-η⁵Cyclopentadienyl group) dimethylsilane] dimethyl titanium, [(N- phenyl acylaminos) (tetramethyl-η⁵Cyclopentadienyl group) dimethylsilane] dimethyl titanium, [(N- benzyl amides base) (tetramethyl Base-η⁵Cyclopentadienyl group) dimethylsilane] dimethyl titanium, [(N- tert-butylamides base) (η⁵Cyclopentadienyl group) -1,2- ethane Diyl] dimethyl titanium, [(N- tert-butylamides base) (η⁵Cyclopentadienyl group) dimethylsilane] dimethyl titanium, [(N- methyl acyls Amido) (η⁵Cyclopentadienyl group) -1,2- ethane diyl] dimethyl titanium, [(N- methyl acylaminos) (η⁵Cyclopentadienyl group) diformazan Base silane] dimethyl titanium, [(N- tert-butylamides base) (η⁵Indenyl) dimethylsilane] dimethyl titanium, [(N- benzyl amides base) (η⁵Indenyl) dimethylsilane] dimethyl titanium etc..

It as nickel based compound, is not particularly limited, can specifically enumerate：Bis- (triphenylphosphine) nickel of dibromo, dichloro are double (triphenylphosphine) nickel, dibromo diacetonitrile nickel, two benzonitrile nickel of dibromo, dibromo (bis- (diphenylphosphino) ethane of 1,2-) nickel, dibromo (bis- (diphenylphosphino) propane of 1,3-) nickel, dibromo (the double phosphino- ferrocene of 1,1 '-diphenyl) nickel, dimethyl are bis- (diphenylphosphine) Nickel, dimethyl (bis- (diphenylphosphino) ethane of 1,2-) nickel, methyl (bis- (diphenylphosphino) ethane of 1,2-) nickel tetrafluoroborate, (2- diphenylphosphino -1- phenyl-ethylenes oxygroup) phenylpyridine nickel, bis- (triphenylphosphine) palladiums of dichloro, dichloro formonitrile HCN palladium, The double tetrafluoroborate of dichlorodiethyl nitrile palladium, dichloro (bis- (diphenylphosphino) ethane of 1,2-) palladium, bis- (triphenylphosphine) palladiums, it is bis- (2, 2 '-bipyridyls) methyl iron tetrafluoroborate etherate etc..

As the specific of the transistion metal compound with ring-type η associativity anion ligands used in present embodiment Example, can also enumerate has " dimethyl " part in the title of the above-mentioned each zirconyl compound and ti-based compound enumerated (it is the part among the title of each compound, i.e., immediately in the part that occurs of part front for being known as " zirconium " or " titanium ", be with X in previously described formula 9⁴The corresponding title in part) instead of " dichloro ", " dibromo ", " diiodo- ", " diethyl ", " dibutyl ", " diphenyl ", " dibenzyl ", " 2- (N, N- dimethylamino) benzyl ", " 2- butene-1s, 4- diyls ", " trans--η of s-⁴-1,4- Diphenyl -1,3- butadiene ", " trans--η of s-⁴- 3- methyl-1,3-pentylenes ", " trans--η of s-⁴- 1,4- dibenzyl -1,3- fourths Diene ", " trans--η of s-⁴- 2,4- hexadienes ", " trans--η of s-⁴- 1,3- pentadienes ", " trans--η of s-⁴Xylyl-1-1,4-, 3- butadiene ", " trans--η of s-⁴Bis- (the trimethyl silyl) -1,3- butadiene of -1,4- ", " cis--η of s-⁴- 1,4- diphenyl- 1,3- butadiene ", " cis--η of s-⁴- 3- methyl-1,3-pentylenes ", " cis--η of s-⁴- 1,4- dibenzyl -1,3- butadiene ", " cis--the η of s-⁴- 2,4- hexadienes ", " cis--η of s-⁴- 1,3- pentadienes ", " cis--η of s-⁴- 1,4- xylyl -1,3- fourths two Alkene ", " cis--η of s-⁴The change of title obtained from any one of bis- (the trimethyl silyl) -1,3- butadiene of -1,4- " etc. Close object.

The transistion metal compound with ring-type η associativity anion ligands used in present embodiment can generally make It is synthesized with well known method.These transistion metal compounds may be used alone, can also be used in combination in present embodiment.

Hereinafter, forming performance catalytic activity for that can be reacted with the transistion metal compound used in present embodiment The activator (hereinafter referred to as " activator ") of complex compound illustrate.

As the activator in present embodiment, such as compound defined in formula 10 below can be enumerated.

[L²-H]^d+[M⁵ _mQ_p]^d-Formula 10

In formula, [L²-H]^d+Indicate the Bronsted acid for protic, wherein L²Indicate neutral lewis base, d 1 ~7 integer；[M⁵ _mQ_p]^d-The noncoordinating property anion for indicating compatibility, here, M⁵Expression belongs to the 5th race~15th of periodic table The metal or nonmetallic of the arbitrary family of race, Q are each independently selected from by two hydrocarbon of hydride, halide, carbon atom number 2~20 The substituted alkyl of base amide groups, the oxyl of carbon atom number 1~30, the alkyl of carbon atom number 1~30 and carbon atom number 1~40 The group of composition, wherein the number of the Q as halide is 1 hereinafter, the integer that m is 1~7, the integer that p is 2~14, d definition are same On, p-m=d.

It as noncoordinating property anion, is not particularly limited, can specifically enumerate tetraphenyl boride, three (to toluene Base) (phenyl) boride, three (pentafluorophenyl group) (phenyl) borides, three (2,4- 3,5-dimethylphenyls) (hydroxyphenyl) borides, three (3,5- 3,5-dimethylphenyls) (phenyl) boride, three (3,5- bis- (trifluoromethyl) phenyl) (phenyl) borides, three (phenyl-pentafluorides Base) (cyclohexyl) boride, three (pentafluorophenyl group) (naphthalene) borides, four (pentafluorophenyl group) borides, triphenyl (hydroxyphenyl) Boride, diphenyl two (hydroxyphenyl) boride, triphenyl (2,4- dihydroxy phenyls) boride, three (p-methylphenyl) (oxybenzenes Base) boride, three (pentafluorophenyl group) (hydroxyphenyl) borides, three (2,4- 3,5-dimethylphenyls) (hydroxyphenyl) borides, three (3,5- 3,5-dimethylphenyl) (hydroxyphenyl) boride, three (3,5- bis- (trifluoromethyl) phenyl) (hydroxyphenyl) borides, three (pentafluorophenyl groups) (2- hydroxyethyls) boride, three (pentafluorophenyl groups) (4- hydroxybutyls) boride, three (pentafluorophenyl groups) (4- hydroxy-cyclohexyls) Boride, three (pentafluorophenyl groups) (4- (4 '-hydroxy phenyl) phenyl) boride, three (pentafluorophenyl groups) (6- hydroxyl -2- naphthalenes) boron Compound etc..

As the example of other preferred noncoordinating property anion, can enumerate the hydroxyl of foregoing illustrative boride by Boride after the displacement of NHR bases.Wherein, R is preferably methyl, ethyl or tertiary butyl.

In addition, as the Bronsted acid for protic, be not particularly limited, can specifically enumerate triethyl ammonium, The trialkyls substituted type ammonium cations such as tripropyl ammonium, three normal-butyl ammoniums, trimethyl ammonium, tributyl ammonium and three n-octyl ammoniums；N,N- Dimethyl puratized agricultural spray, N, N- diethyl puratized agricultural spray, N, N, 2,4,6- pentamethyls puratized agricultural spray, N, the N such as N- dimethyl benzyl puratized agricultural sprays, N- dialkyl group Puratized agricultural spray cation；The dialkyl ammonium cations such as two (isopropyl) ammoniums, dicyclohexyl ammonium；TriphenylThree (aminomethyl phenyls) Three (3,5-dimethylphenyls)Equal triarylsCation；Or dimethyl sulfonium, diethyl sulfonium, diphenyl sulfonium etc..

In addition, in present embodiment, as activator, the organic of the unit indicated with formula 11 below can also be used Metal oxo-compound.

Here, M⁶For the metal or metalloid of the race of belonging to group 13 of periodic table~the 15th, R¹⁴Be each independently carbon atom number 1~ 12 alkyl or substituted alkyl, n are metal M⁶Valence mumber, m be 2 or more integer.

The preference of the activator of present embodiment is, for example, the organo-aluminium oxygroup of the unit indicated with formula 12 below Compound.

Here, R¹⁵For the alkyl of carbon atom number 1~8, the integer that m is 2~60.

The more preferable example of the activator of present embodiment is, for example, the methyl alumina of the unit indicated with formula 13 below Alkane.

Here, the integer that m is 2~60.

In present embodiment, activator component may be used alone, can also be used in combination.

In present embodiment, these catalyst components can be supported on solid constituent and be used as loaded catalyst. It as such solid constituent, is not particularly limited, can specifically enumerate：Polyethylene, polypropylene or styrenedivinyl The porous polymer materials such as the copolymer of benzene；Silica, aluminium oxide, magnesia, magnesium chloride, zirconium oxide, titanium oxide, oxidation The periodic tables such as boron, calcium oxide, zinc oxide, barium monoxide, vanadic anhydride, chromium oxide and thorium oxide the 2nd, 3,4,13 and 14 races member The solid inorganic material of element；And their mixture；And at least one inoganic solids selected from their composite oxides Material.

It as the composite oxides of silica, is not particularly limited, can specifically enumerate：Silica-magnesia, The silica such as silica-alumina and the 2nd race of periodic table or the composite oxides of the 13rd race's element.In addition, this embodiment party In formula, other than above two catalyst component, organo-aluminum compound can be used as catalyst component as needed.This The organo-aluminum compound that can be used in embodiment is, for example, the compound that formula 14 below indicates.

AlR¹⁶ _nX⁵ _3-n... formula 14

Here, R¹⁶For the alkyl of carbon atom number 1~12, the aryl of carbon atom number 6~20, X⁵For halogen, hydrogen or alkoxy, Alkyl is straight chained alkyl, branched alkyl or cyclic alkyl, the integer that n is 1~3.

Here, organo-aluminum compound can be the mixture for the compound that above-mentioned formula 14 indicates.As in present embodiment The organo-aluminum compound that can be used can enumerate R in for example above-mentioned formula¹⁶For methyl, ethyl, butyl, isobutyl group, hexyl, pungent Base, decyl, phenyl, tolyl etc., in addition, as X⁵, methoxyl group, ethyoxyl, butoxy, chlorine etc. can be enumerated.

It as the organo-aluminum compound that can be used in present embodiment, is not particularly limited, can specifically enumerate：Three Aluminium methyl, triethyl aluminum, tri-butyl aluminum, triisobutyl aluminium, three hexyl aluminium, trioctylaluminum, tridecyl aluminum etc. or these are organic The reaction product of the alcohols such as aluminium and methanol, ethyl alcohol, butanol, amylalcohol, hexanol, octanol, decyl alcohol, such as dimethyl aluminum methoxide, two Ethyl aluminum ethoxide, dibutyl butoxy aluminium etc..

The example of the polymerization of polyethylene as present embodiment can be enumerated poly- by suspension polymerization or gas phase It is legal by the monomer (co) polymerization containing ethylene, be preferably able to effectively remove heat of polymerization suspension polymerization.In suspension polymerization In, unreactive hydrocarbons medium can be used as medium, in addition, alkene itself can also be used as solvent use.

As the unreactive hydrocarbons medium, be not particularly limited, can specifically enumerate propane, butane, iso-butane, pentane, The aliphatic hydrocarbons such as isopentane, hexane, heptane, octane, decane, dodecane, kerosene；The alicyclic rings such as pentamethylene, hexamethylene, methyl cyclopentane Hydrocarbon；The aromatic hydrocarbon such as benzene,toluene,xylene；The halogenated hydrocarbons such as chloric ethane, chlorobenzene, dichloromethane；Or their mixture etc..

Polymerization temperature in the polymerization of the polyethylene of present embodiment be preferably generally 30 DEG C or more and 100 DEG C hereinafter, into One step is preferably 35 DEG C or more and 90 DEG C hereinafter, particularly preferably 40 DEG C or more and 80 DEG C or less.Polymerization temperature is if it is 30 DEG C More than, then it industrially can effectively manufacture.On the other hand, polymerization temperature if it is 100 DEG C hereinafter, then can continuously stablize Operating.

Polymerization pressure in the polymerization of the polyethylene of present embodiment is preferably generally normal pressure or more and 2MPa hereinafter, more excellent 0.1MPa or more is selected as and 1.5MPa hereinafter, further preferably 0.2MPa or more and 1.0MPa are hereinafter, especially more preferably 0.3MPa or more and 1.0MPa it is below under the conditions of.Polymerisation can be by intermittent, semi continuous, continuous any one Kind method carries out.

Furthermore it is possible to which polymerization is divided into the different progress of more than two stages of reaction condition.In addition, for example, as West Germany is special Profit application discloses described in No. 3127133 specification, and the molecular weight of obtained polyethylene can be by making in polymerization system There are hydrogen or makes polymerization temperature variations and adjust.It is used as chain-transferring agent by adding hydrogen in polymerization system, can incites somebody to action In molecular weight control to appropriate range.When adding hydrogen in polymerization system, the molar fraction of hydrogen be preferably 0mol% with Upper and 30mol% hereinafter, more preferably 0mol% or more and 25mol% hereinafter, further preferably 0mol% or more and 20mol% or less.Can also include total to ultra-high-molecular-weight polyethylene other than above-mentioned each ingredient in addition, in present embodiment Polymers manufactures useful other well known ingredient.

[manufacturing method of polyethylene powder]

The manufacturing method of the polyethylene powder of present embodiment include by preceding method obtain polyethylene powder process, Make process that catalyst for olefines polymerizing inactivates and by the process of polyethylene powder drying.

The polyethylene powder of present embodiment, from the viewpoint of Continuous maching productivity, product size stability, wherein The number for the aluminium hydroxide that minor axis is 50 μm or more is 10 or less in polyethylene powder 500g.Such polyethylene powder can Suitably to be obtained by the following method.

In order to make the number that the minor axis of present embodiment is 50 μm or more of aluminium hydroxide be in polyethylene powder 500g 10 reduce the minor axis of aluminium hydroxide contained in polyethylene powder or reduce minor axis as 50 μm or more hereinafter, can enumerate The method of the number of aluminium hydroxide.As its method is realized, the system reduced in the polymerization including polyethylene powder can be enumerated Make the size of the aluminium hydroxide generated in process.

For this purpose, the manufacturing method as polyethylene powder, can enumerate

(1) leniently implement from the side of the inactivation of co-catalysts such as the reactive species of catalyst or excessive alkyl aluminum Method；

(2) continuously without intermittently implementing the mistake from the co-catalysts such as the reactive species of catalyst or excessive alkyl aluminum Method living；

(3) method for reducing the input concentration of co-catalyst；

(4) method for reducing amount of moisture contained in solvent

(5) method for reducing amount of moisture contained in ethylene or hydrogen etc.；

Deng.Hereinafter, being illustrated to each method.

Method (1)

As the side for leniently implementing the inactivation from the co-catalysts such as the reactive species of catalyst or excessive alkyl aluminum Method, the method for specifically preferably leniently carrying out the charging of deactivator.For example, when selecting water as deactivator, be not preferably by Water droplet is added drop-wise in the powder after polymerization, but the method being blown to the powder after polymerization with vaporous.In addition, as leniently The method of implementation can be enumerated and further dilute vaporish moisture with inert gases such as nitrogen.In addition, if that will inactivate While agent is blown in the form of vaporous or vaporous and the mixed gas of inert gas, while to polyethylene powder Body is stirred, then further can leniently be inactivated.As a result, the size of the aluminium hydroxide of generation can be reduced.

Can be after the polymerization of polyethylene powder, with processing such as alcohol, then only with nitrogen etc. in addition, as another method The method that inert gas is dried.Specifically, adding a certain amount of alcohol (such as first in slurry after polyethylene polymerization Alcohol, ethyl alcohol etc.) carry out used in catalyst or co-catalyst inactivation, after solvent is detached with polyethylene powder, in drying The method being dried using inert gas flows such as nitrogen in machine.

Method (2)

As continuously without intermittently implementing from the co-catalysts such as the reactive species of catalyst or excessive alkyl aluminum The method of inactivation specifically illustrates as follows.That is, as described in method (1), when selecting feed process of the steam as deactivator, no It is intermittently to feed, but use pressure-regulating valve, under pressure by steam or the gaseous mixture of steam and inert gas The method that the deactivators such as body are supplied to the powder after polymerization.At this point, if it is continous way polymerization process, then it is right under a certain pressure The polymerization powder of certain flow rate supplies a certain amount of deactivator and is important, and if it is batch polymerization process, is then fully stirring In the state of mixing mixing, under a certain pressure to after polymerization slurry or powder supply a certain amount of deactivator and be important.

Method (3)

As the method for the input concentration for reducing co-catalyst, can enumerate in advance with solvent by the co-catalyst in storage tank It dilutes and prepares the method for low concentration co-catalyst solution, the method for the feed rate for reducing co-catalyst.

Method (4)

As the method for reducing amount of moisture contained in solvent, can enumerate makes solvent remove or subtract bys molecular sieve etc. The method of moisture contained in few solvent.

Method (5)

As the method for reducing amount of moisture contained in ethylene or hydrogen etc., can be enumerated in the same manner as method (4) makes second The method that alkene or hydrogen etc. are removed bys molecular sieve etc. or reduces contained humidity.

In addition, the method as the aluminium hydroxide number for reducing 50 μm of minor axis or more, can enumerate in polyethylene powder Add the mixed solvent (volume ratio 3 of chloroform or chloroform and ethyl alcohol:1) progress such as mechanical agitator with stirring blade, are utilized Then stirring stops stirring, stand, the method that the polyethylene powder of floating is detached with sediment.

The polyethylene powder of present embodiment, from the viewpoint of operation or dissolubility in a solvent, preferably coarse powder is few. Coarse powder can utilize appropriate screen out.It is, for example, possible to use 250 μm of aperture, 300 μm, 355 μ based on JIS Z8801 standards M, 425 μm, 500 μm, 600 μm, 710 μm or 850 μm of sieve is removed unsanctioned substance as coarse powder.

Magnesium element content contained in polyethylene powder about the present invention, can pass through 1. polymerization activity, 2. co-catalysis Dosage controls.For example, if reducing 1. polymerization activity, contained magnesium amount can be increased.Specifically, in order to reduce polymerization Activity, preferably reduce polymerization temperature, reduce polymerization pressure, reduce the residence time etc..On the other hand, using organic-magnesium as 2. helping When catalyst, by increasing its usage amount, contained magnesium amount can be increased.On the contrary, being urged if organo-aluminium conduct is mainly used to help Agent can then reduce used organic magnesium amount.

Based on above-mentioned, when reducing contained magnesium amount, countermeasure contrary to the above is preferably taken.Therefore, this Shen is being improved When the fracture of wire that please be invent, it is important containing magnesium amount appropriate by suitably controlling polymerizing condition.

[other ingredients]

The polyethylene powder of present embodiment can be applied in combination as needed with well known various additives.As hot steady Determine agent, such as four [methylene (3,5- di-t-butyl -4- hydroxyls) hydrogen cinnamate] methane, distearyl thio two can be enumerated The heat-resisting stabilizing agents such as propionic ester or bis- (2,2 ', 6,6 '-tetramethyl -4- piperidines) sebacates, 2- (2- hydroxy tert-butyls -5- Aminomethyl phenyl) weathering stabilizers such as -5- chlorobenzotriazoles etc..In addition, as colorant, inorganic, organic can be added Dry color.Furthermore it is also possible to enumerate as calcium stearate, magnesium stearate, tristearin well known to lubricant or chlorine hydride absorbent etc. The stearate such as sour zinc are as suitable additive.

[purposes]

The polyethylene powder of present embodiment has high Continuous maching productivity and product size stability.Therefore, pass through Various processing methods can be applied to various uses.For example, being suitable as secondary cell diaphragm use, particularly lithium secondary battery Diaphragm use, high strength fiber Wesy, microporous barrier is used or gel spinning is used.Specifically, by using in the damp process of solvent, utilization Extruder with T shape die heads can obtain microporous barrier by the processing method of extrusion, stretching, extraction, drying.It is such micro- Pore membrane can be suitable for using lithium rechargeable battery and lead accumulator as the secondary cell diaphragm, particularly lithium ion of representative Secondary battery membrane.In addition, by using it is in the damp process of solvent, using the extruder with circular die by being extruded as Gel, stretching, extraction, drying processing method obtain silk, and the processing method that it is further stretched, it is hereby achieved that High strength fibre.Such high strength fibre can be used for setline, Anti-thorn gloves, ship rope, bullet-proof vest, plate armour Bulletproof cover, fishnet, sports goods, suture of vehicle etc..

Add in addition, the polyethylene powder of present embodiment can also carry out extrusion molding, compression moulding, thermal sintering etc. Work.By these processing, the gear or roller, curtain rail, bullet using previous High molecular weight polyethylene powder can be used for The increasing of the liner of the warehouse of guide rail, the cereal of bulbec etc., rubber product slide coating, skiing plate material and ski boots bottom, truck or The purposes such as gasket material, filter, the dedusting material of the heavy-duty machineries such as forklift.

Embodiment

Hereinafter, the present invention is described in more detail by embodiment, but the present invention is not by any restrictions of following embodiment.

[assay method and condition]

(1) molecular weight (viscosity average molecular weigh：Mv)

The viscosity average molecular weigh of High molecular weight polyethylene powder passes through method as shown below according to ISO1628-3 (2010) It finds out.First, 20mg polyethylene is added in the naphthalane of 20mL (decahydronaphthalenes), being stirred 2 hours at 150 DEG C keeps polymer molten Solution.By the solution in 135 DEG C of thermostat using Cannon-Fenske viscosimeters (Chai Tian instruments for scientific research industrial group manufacture, Product number -100), measure the lowering time (t between graticule_s).As blank, polyethylene is not added, naphthalane is measured and individually falls Lower time (t_b).Similarly, the weight for changing polyethylene measures reduced viscosity.The ratio of the polymer found out according to the following formula is dense viscous Spend (η_sp/ C) it maps respectively, derive concentration (C) (unit：G/dL) with the reduced viscosity (η of polymer_sp/ C) linear equation, And find out the limiting viscosity ([η]) for being extrapolated to concentration 0.

η_sp/ C=(t_s/t_b- 1)/0.1 (unit：dL/g)

Then, using following formula A viscosity average molecular weigh (Mv) is calculated using the value of above-mentioned limiting viscosity [η].

Mv=(5.34 × 10⁴)×[η]^1.49Mathematical expression A

(2) number of aluminium hydroxide

500mL ethyl alcohol is put into the glass system beaker of 3L, uses the teflon paddle with long 75mm, depth 22mm The mechanical agitator of piece, is stirred with 200rpm at normal temperatures.Polyethylene powder 500g is slowly put into thereto, after input Continue stirring 10 minutes.Then, 1500mL chloroforms are put into while agitating, are stirred for 10 minutes.Then, stop stirring, it is quiet .5~2.0 hour are set to 0, with the naked eye confirm to be mainly the floating of polyethylene powder.Gently with the made of metal net of aperture 54 μm (280 mesh) Ground picks up the polyethylene powder of the floating and removes.Then, supernatant is abandoned by being decanted, continuation is lightly decanted until burning Solution residual quantity in cup reaches about 50mL~about 100mL, and supernatant is abandoned.Remaining solution is determined using about 10mL chloroforms It is transferred in the glass system beaker of 200mL to amount, stands again.Amount of solution is adjusted to about 50mL by decantation gently again, And it is transferred in separatory funnel.It is stood in separatory funnel again, lower part solution (including sediment) about 10mL~about 20mL is protected There are in glass system screwed pipe.It is covered with filter paper in order not to allow dust to enter screwed pipe, setting to leading to exhaust equipment Diel makes evaporation of the solvent in wind devices.It is dried in vacuo at normal temperatures again.

The sediment of the recycling is taken, sample is all using SEM-EDX (scanning electron microscopes-energy dispersion type X-ray Analytical equipment：Hitachi, Ltd manufactures, product name SU-70) it measures.In the aluminium hydroxide observed using SEM, minor axis is less than 50 μm Aluminium hydroxide except, the aluminium hydroxide of 50 μm of minor axis or more is counted, the number of the aluminium hydroxide is found out.In addition, by upper The method of stating do not confirm the sediment of 50 μm of minor axis or more there are the case where " 1 is denoted as in table>”.

(3) aluminium element content

Using microwave decomposition device (manufacture of model ETHOS TC, マイ Le ストー Application ゼネラ Le company) by polyethylene Powder pressing decomposes, and by internal standard method, utilizes ICP-MS (inductivity coupled plasma mass spectrometry device, 7 , サー of model X series of X モ Off ィッシャーサイエ Application ティフィック companies manufacture, detection limit 0.01ppm) measure polyethylene powder in aluminium element Content.

(4) magnesium element content

Using microwave decomposition device (manufacture of model ETHOS TC, マイ Le ストー Application ゼネラ Le company) by polyethylene Powder pressing decomposes, and by internal standard method, utilizes ICP-MS (inductivity coupled plasma mass spectrometry device, 7 , サー of model X series of X モ Off ィッシャーサイエ Application ティフィック companies manufacture, detection limit 0.01ppm) measure polyethylene powder in magnesium elements Content.

(5) Continuous maching productivity

The Continuous maching productivity of (5) -1 films

Pentaerythrite four [3- (3,5- di-t-butyl -4-s of the 1 mass % as antioxidant is added in polyethylene powder Hydroxy phenyl) propionic ester], carried out using drum mixer dry-mixed, thus obtain the mixtures such as polymer.By obtained polymerization The mixtures such as object nitrogen is supplied in double screw extruder into after line replacement by feeder in a nitrogen atmosphere.In addition, utilizing By atoleine, (dynamic viscosity at 37.78 DEG C is 7.59 × 10 to plunger pump^-5m²/ s) it is injected into extruder barrel.Adjust into Glassware and pump so that the amount ratio in all compositions of melting mixing and extrusion shared by Liquid Paraffin is 65 mass %, polymerize A concentration of 35 mass % of object.It is carried out under the conditions of following melting mixing：200 DEG C of set temperature, screw speed 240rpm, discharge rate 12kg/ hours.

Then, melting mixing object is cast to via T shape die heads extrusion in surface temperature control to 25 DEG C of chill roll, by This obtains the gel film of 1400 μm of original film thickness.At this point, in the upstream side of T shape die heads, overlapping is used based on JIS Z8801 standards 150 μm, 53 μm and 150 μm of aperture stainless steel plain weave silk screen, measure its resin pressure most nearby using pressure gauge.And And according to evaluation criteria below, evaluate Continuous maching productivity.That is, by squeeze out start after by 1 hour when resin pressure (P₀) it is used as benchmark, when by being set as P by the resin pressure of certain time, increment rate of such as giving a definition.

Increment rate (%)=(P-P₀)/P₀×100

◎：The increment rate of resin pressure after 120 hours is within ± 5%.

○：The increment rate of resin pressure after 72 hours is the increment rate of 5% or less and the resin pressure after 120 hours More than 5% and within 10%.

△：The increment rate of resin pressure after 72 hours is the increase of 5% or less and the resin pressure after 120 hours Rate is more than 10%.

×：The increment rate of resin pressure after 72 hours is more than 5%.

(5) -2 Continuous maching productivities

Pentaerythrite four [3- (3,5- di-t-butyls-of the 0.3 mass % as antioxidant is added in polyethylene powder 4- hydroxy phenyls) propionic ester], carried out using drum mixer dry-mixed, thus obtain the mixtures such as polymer.It will be obtained poly- Closing the mixtures nitrogen such as object, (dynamic viscosity at 37.78 DEG C is into atoleine after line replacement, is put into mixing channel in advance 7.59×10^-5m²/ s) make a concentration of 8 mass % of polymer, and be stirred at room temperature, thus obtain uniform slurry.It will It is supplied in double screw extruder in a nitrogen atmosphere with pump, carries out melting mixing.It is carried out under the conditions of following melting mixing： 250 DEG C of set temperature, screw speed 200rpm, discharge rate 12kg/ hours.Stablize to assign discharge in the downstream side of extruder Property, 250 μm, 106 μm, 45 μm, 106 μm and 250 μm of the aperture based on JIS Z8801 standards is overlapped not by gear pump Become rusty steel plain weave silk screen.Its resin pressure most nearby is measured using pressure gauge.Then, by spinning die head, gel is processed Spinning.Also, according to evaluation criteria below, evaluate Continuous maching productivity.That is, by squeeze out start after by 1 hour when Resin pressure (P₀) it is used as benchmark, when by being set as P by the resin pressure of certain time, increment rate of such as giving a definition.

Increment rate (%)=(P-P₀)/P₀×100

◎：The increment rate of resin pressure after 120 hours is within ± 5%.

×：The increment rate of resin pressure after 72 hours is more than 5%.

The Continuous maching productivity of (5) -3 films

Using material polyethylene powder, spherical powder shaped the silicon dioxide granule (" Hi-Sil of PPG companies manufacture is used SBG ") be used as inorganic filler, with relative to 40 mass parts polyethylenes and 60 mass parts silicon dioxide granules for 140 mass parts Ratio adding liquid paraffin, the aperture of stainless steel plain weave silk screen is 180 μm, 150 μm, 180 μm, in addition to this, with (5) -1 Similarly it is configured to gel piece.The resin pressure of the silk screen most nearby is measured using pressure gauge.Also, according to evaluation below Benchmark evaluates Continuous maching productivity.That is, by squeeze out start after by 1 hour when resin pressure (P₀) it is used as benchmark, it will be through When crossing the resin pressure of certain time and being set as P, increment rate of such as giving a definition.

Increment rate (%)=(P-P₀)/P₀×100

◎：The increment rate of resin pressure after 120 hours is within ± 5%.

×：The increment rate of resin pressure after 72 hours is more than 5%.

(6) product size stability

(6) -1 film thickness stabilities

By in the gel film setting to twin shaft tentering stretching-machine simultaneously of 1400 μm of the original film thickness obtained in (5) -1, carry out It is biaxial stretch-formed.Stretching condition is set as 7.0 times of MD multiples, 7.0 times of TD multiples (i.e. 7 × 7 times), 125 DEG C of biaxial stretch-formed temperature.So Afterwards, it is fully impregnated into methyl ethyl ketone slot in methyl ethyl ketone and removes atoleine to extract, then dry and remove methyl ethyl ketone.

Then, it is arranged into TD stenters to carry out heat setting, in 125 DEG C of heat setting temperature, 1.4 times of draw ratio Under conditions of carry out heat setting, then carry out 0.8 times of loose operations (that is, heat set relaxation rate be 0.8 times).Obtained by herein Film thickness be about 20 μm.The film is cut into TD × MD (30cm × 30cm) size, obtains microporous barrier.To the film, with substantially etc. Interval using film thickness measuring instrument (テクロック companies manufacture, model SM-1201) measure four points on angle, each side central portion 1 four points, central portion point add up to the film thickness of 9 points.Using the three pieces film of above-mentioned size, the film thickness for adding up to 27 points is measured. The maximum value of film thickness in 27 points is set as T (max), when minimum value is set as T (min), average value is set as T (ave), following institute Definition uneven thickness is stated, criterion below is based on, evaluates film thickness stability.

(uneven thickness) (%)=(T (max)-T (min))/(2 × T (ave)) × 100

○：Uneven thickness (%) is 0% or more and 2% or less

△：Uneven thickness (%) is more than 2% and 4% or less

×：Uneven thickness (%) is more than 4%

(6) -2 string diameter stability

The gel spinning obtained in (5) -2 is used, using the trichorotrifluoroethane (TCTFE) of reflux cable-styled (Sohxlet) in device atoleine is extracted from the gel spinning.Then, gel is spinned and air-dries and generates xerogel, Start, at 120 DEG C, two step hot-stretch then to be carried out at 150 DEG C.About draw ratio, to gel spinning and xerogel spinning progress It is maximized in each step stretched, total draw ratio is set as 500 times.

Obtained silk is cut out 1 meter, in the equally spaced positions basic 10cm, is measured except two ends using light microscope The string diameter of 9 points other than end.By the total measurement 4 of 1 meter of silk, the string diameter for adding up to 36 points is measured, maximum value is set as T (max), when minimum value is set as T (min), average value is set as T (ave), the string diameter as described below that defines is uneven, is based on judgement below Standard evaluates string diameter stability.

(string diameter is uneven) (%)=(T (max)-T (min))/(2 × T (ave)) × 100

○：String diameter unevenness (%) is 0% or more and 3% or less

△：String diameter unevenness (%) is more than 3% and 5% or less

×：String diameter unevenness (%) is more than 5%

(6) -3 film thickness stabilities

The gel film obtained in (5) -3 is used, then makes it through and carves the regulation equipped with reinforcing rib formation on a roller It is formed between the forming rolls of the ditch of shape/predetermined size, to obtain the piece of specific thickness, regulation shape.Then, by the piece It is impregnated into n-hexane, extraction removes the atoleine in described of specified amount, and is dried, to obtain microporous barrier. During microporous barrier is formed, the powder shaped silicon dioxide granule of three-dimensional chain connection structure in the three-dimensional net structure of polyvinyl resin Being mixed for homogeneously dispersed state and form three-dimensional net structure.The content of atoleine is 13 mass %.In addition, for one The substrate thickness that the straight line reinforcing rib that a plurality of reinforcement height is 0.65mm is parallelly provided projectingly on a face is 0.25mm, wraps Include the microporous barrier that the overall thickness including reinforcing rib is 0.90mm.The film is cut into TD × MD (30cm × 30cm) size, is obtained To microporous barrier.To the film, film thickness measuring instrument (テクロック companies manufacture, model SM-1201) is used to measure to be generally equally 1 four points, four points of central portion on each side, central portion point add up to the film thickness of 9 points on angle.Use the three pieces of above-mentioned size Film measures the film thickness for adding up to 27 points.The maximum value of film thickness in 27 points is set as T (max), minimum value is set as T (min), flat When mean value is set as T (ave), uneven thickness is defined as described below, is based on criterion below, evaluates film thickness stability.

(uneven thickness) (%)=(T (max)-T (min))/(2 × T (ave)) × 100

○：Uneven thickness (%) is 0% or more and 2% or less

△：Uneven thickness (%) is more than 2% and 4% or less

×：Uneven thickness (%) is more than 4%

(7) acid resistance

In the case of film, it is cut into the size of 90mm × 5cm.In the case of silk, it is cut into the length of 90mm, utilizes monofilament It is evaluated.Each comfortable 80 DEG C, impregnate 3 days in the aqueous sulfuric acid of 40 mass %, measure the front and back tensile strength of dipping, and base Judge acid resistance in criterion below.In tension test, film according to ISO527-3 standards, silk according to ISO2062 standards into Row measures.Tensile strength before dipping is set as TS₀, the tensile strength after dipping be set as TS₁。

Strength retention (%)=TS₁/TS₀×100

○：Strength retention is 90% or more.

△：Strength retention is less than 90%.

(8) resistance to fracture of wire

By with (5) -2 shown in method similarly operate processed filament when, continuously operate 2 hours, fracture of wire occurs therebetween In the case of, its number is counted, spinning is again continued to, start the required time deducts from 2 hours, purely can continuously transport The total ascent time turned implemented for 2 hours modes.The number of fracture of wire therebetween is added up to.Implement a series of fortune twice Turn, respective fracture of wire number is averaged.Using the fracture of wire number average value, resistance to fracture of wire is evaluated according to following criterions Property.

○：Fracture of wire number average value is 0 time

△：Fracture of wire number average value is more than 0 time and is 1.5 times or less

×：Fracture of wire number average value is more than 1.5 times

[reference example] catalyst synthesis example

[preparation of solid catalyst component [A]]

1600mL hexanes are added in the 8L stainless steel autoclaves after fully carrying out nitrogen displacement.That is stirred at 10 DEG C is same When with 4 hours simultaneously add 1mol/L titanium tetrachloride hexane solution 800mL and 1mol/L composition formula AlMg₅(C₄H₉)₁₁ (OSiH)₂The hexane solution 800mL of the organo-magnesium compound of expression.It after addition, slowly heats up, it is 1 small that at 10 DEG C, the reaction was continued When.After reaction, 1600mL supernatants are removed, is washed five times with 1600mL hexanes, thus prepares solid catalyst component [A].Titanium amount contained in solid catalyst component [A] 1g is 3.05mmol.

[preparation of solid catalyst component [B]]

(1) synthesis of (B-1) carrier

Oneself of the hydroxyl trichlorosilane of 2mol/L is put into the 8L stainless steel autoclaves after fully carrying out nitrogen displacement Composition formula AlMg was added dropwise with 4 hours while stirring at 65 DEG C in alkane solution 1000mL₅(C₄H₉)₁₁(OC₄H₉)₂The organic-magnesium of expression The hexane solution 2550mL (being equivalent to magnesium 2.68mol) of compound, then the reaction was continued while stirred 1 hour at 65 DEG C.Reaction After, supernatant is removed, is washed 4 times with 1800mL hexanes.To the solid ((B-1) carrier) analysis as a result, solid per 1g Magnesium contained in body is 8.31mmol.

(2) preparation of solid catalyst component [B]

With 1 hour while being stirred for 10 DEG C in the hexane slurry 1970mL containing above-mentioned (B-1) carrier 110g The composition formula AlMg of titanium tetrachloride the hexane solution 110mL and 1mol/L of 1mol/L are added simultaneously₅(C₄H₉)₁₁(OSiH)₂It indicates The hexane solution 110mL of organo-magnesium compound.After addition, the reaction was continued at 10 DEG C 1 hour.After reaction, it removes 1100mL supernatants are washed 2 times with 1100mL hexanes, thus prepare solid catalyst component [B].The solid catalyst component Titanium amount contained in [B] 1g is 0.75mmol.

[the preparing metallocene catalyst of solid catalyst component [C]]

(preparation of carrier [C-1])

As the precursor of carrier [C-1], use silica Q6 [Fuji シリシア manufactures].By silica Q6 in nitrogen Heat 5 hours at 400 DEG C under gas atmosphere.The specific surface area of silica Q6 after heat treatment is 480m²/ g, average grain Diameter is 9.5 μm.The surface hydroxyl amount of silica after heat treatment is 1.85mmol/g.Capacity 1.8L after nitrogen displacement In autoclave, so that the silica Q6 (40g) after heat treatment is distributed in hexane 800mL, obtain slurry.The slurry that will be obtained Hexane solution (concentration 1mol/L) 80mL that triethyl aluminum is added while being maintained at 20 DEG C under stiring, is then stirred 2 hours, Prepare the hexane slurry 880mL for the carrier [C-1] for being adsorbed with triethyl aluminum.

(preparation of transistion metal compound [D])

As transistion metal compound (D-1), [(N- tert-butylamides base) (tetramethyl-η is used⁵Cyclopentadienyl group) two Methyl-monosilane] titanium -1,3- pentadienes (hereinafter referred to as " titanium complex ").As organo-magnesium compound (D-2), composition formula is used AlMg₆(C₂H₅)₃(C₄H₉)₁₂(hereinafter referred to as " Mg1 ").In addition, the Mg1 by hexane, at 25 DEG C by specified amount Triethyl aluminum mixes to synthesize with dibutylmagnesium.

Titanium complex 200mmol is dissolved into Isopar E (manufacture of Exxon Chemical companies) 1000mL, is added Hexane solution (concentration 1mol/L) 20mL of Mg1, then add hexane and titanium complex concentration is adjusted to 0.1mol/L, obtain transition Metallic compound ingredient [D].

(preparation of activator [E])

As activating compounds (E-1), three (pentafluorophenyl group) (4- hydroxy benzenes of bis- (hydrogenated tallow alkyl) methyl ammoniums is used Base) boride (hereinafter referred to as " boride ").As (E-2) organo-aluminum compound, diethylaluminium ethoxide is used.By 5.7g Boride, which is added in toluene 50mL, to be dissolved, and the 100mmol/L toluene solutions of boride are obtained.In the toluene of the boride Hexane solution (concentration 1mol/L) 5mL of diethylaluminium ethoxide is added in solution at 25 DEG C, then adds hexane, toluene is molten Boride concentrations in liquid are adjusted to 80mmol/L.Then, it is stirred 1 hour at 25 DEG C, thus prepares activator [E].

(preparation of solid catalyst component [C])

In the slurry 880mL of the carrier [D-1] obtained by aforesaid operations, added simultaneously while being stirred at 20 DEG C Activator [E] 50mL obtained by aforesaid operations and transistion metal compound ingredient [D] 40mL obtained by aforesaid operations continues Reaction 3 hours, thus prepares solid catalyst component [C].

[embodiment 1]

The container type 300L polymer reactors for being continuously fed to hexane, ethylene, hydrogen, catalyst that there is agitating device In.Polymerization pressure is 0.5MPa.Polymerization temperature is maintained at 83 DEG C by chuck cooling.Hexane was supplied with 40L/ hours speed. Using solid catalyst component [A] and as the triisobutyl aluminium of co-catalyst.Solid catalyst component [A] was with 0.2g/ hours Speed be added in polymerizer, triisobutyl aluminium is added to 10mmol/ hours speed in polymerizer.It is polyvinyl Manufacturing speed is 10kg/ hours.Hydrogen, which is continuously fed, with pump so that the density of hydrogen relative to gaseous ethene is 14mol%. Catalyst activity is 80000g-PE/g- solid catalyst components [A].Polymeric size is continuously retracted to pressure 0.05MPa, So that the level of polymer reactor is kept constant in the flash distillation column of temperature 70 C, and by unreacted ethylene and Hydrogen Separation.

Polymeric size makes the level of polymer reactor keep constant continuously through solvent separation process, and send to drying Process.There is no block-like polymer, slurry extraction conduit is also unplugged, can steadily continuously run.

In addition, in inactivation/drying process, to the powder after polymerization steam and nitrogen mixed gas flow 20Nm³/ Implement the inactivation of catalyst and co-catalyst under conditions of hour.It is stearic that 1500ppm is added in obtained polyethylene powder Sour calcium (big day chemistry corporation is made, C60), is equably mixed using Henschel mixer.Obtained ethene polymers Powder uses the sieved sieve in 425 μm of aperture, will not removed by the powder of sieve.Using the polyethylene powder obtained in this way as PE1. Each characteristic is measured according to above-mentioned method, the results are shown in Table 1.

(identification of aluminium hydroxide)

In addition, using the sediment obtained from PE1 according to the method for above-mentioned (2) as sample, infrared absorption spectrum is measured, it should Spectrogram (a) such as Fig. 1 institutes method.In addition, the use of the IR-410 of Japanese light splitting company manufacture being type, ATR methods (Dura is utilized Scope (ATR crystallization plates：Diamond/ZnSe)), in resolution ratio 4cm^-1, implement to measure under conditions of scanning number 32 times.In order to than Compared with, using the aluminium hydroxide that Sigma-Aldrich companies manufacture as standard substance, infrared absorption spectrum is similarly measured, Spectrogram (b) is as shown in Figure 1.In addition, as standard substance, the aluminium oxide manufactured using three Tianjin and chemical company is similarly surveyed Determine infrared absorption spectrum, spectrogram (c) is as shown in Figure 1.As known from the above, the sediment obtained from PE1 observes source In the minor peaks (d) of polyethylene, main component is not aluminium oxide, but aluminium hydroxide.

In addition, using PE1, according to the method described in the Continuous maching productivity of (5) -1 films, original film thickness 1400 is obtained μm gel film, evaluate Continuous maching productivity.In addition, using the gel film of 1400 μm of the original film thickness obtained in this way, according to Method described in (6) -1 film thickness stabilities evaluates dimensional stability, and the method evaluation described in (7) acid resistance is acidproof Property.The Continuous maching productivity of (5) -1 films, (6) -1 film thickness stabilities and (7) acid proof evaluation result are as shown in table 1.

(usability of the diaphragm as lithium secondary battery)

As electrolyte, the LiPF of concentration 1.0mol/L is used₆Ethylene carbonate：Methyl ethyl carbonate=1：2 (volumes Than) mixed solution.As cathode, using artificial graphite as main component, as anode, lithium cobalt composite oxide is used LiCoO₂As main component, obtained microporous barrier is reused, is laminated with the sequence of cathode, microporous barrier, anode, microporous barrier Afterwards, wind 12 times it is spiral, thus make plate electrode layer stack.By the plate electrode layer stack under 70 DEG C of temperature condition 2MPa, it is pressed into tabular under the conditions of 30 seconds, obtains battery winding body.Then, the battery winding body of making is inserted into aluminum The inside of battery can.Then, chamber wall will be connected to by aluminum lead derived from anode, nickel lead will connected derived from cathode It is connected to the lid portion of terminal of battery can.Then, nonaqueous electrolytic solution and closed is injected in the battery can.The lithium-ion electric made in this way Pond is used as that the secondary cell of charge and discharge cycles can be carried out.Therefore, obtained microporous barrier can be used as lithium rechargeable battery Diaphragm use.

[embodiment 2]

The density of hydrogen of ethylene relative to gas phase is 5mol%, adds 500ppm calcium stearate (big day chemistry corporations Make, C60), in addition to this, polyethylene powder (PE2) is obtained by operation similarly to Example 1.It surveys similarly to Example 1 Determine various characteristics, the results are shown in Table 1.

[embodiment 3]

It uses and PE1/PE2 is replaced by PE1 with the powder that 50 mass of mass %/50 % are obtained by mixing with Henschel mixer As material polyethylene powder, in addition to this, implement similarly to Example 1.Various characteristics are measured similarly to Example 1, are tied Fruit is as shown in table 1.

[embodiment 4]

Using solid catalyst component [B], polymerization temperature is set as 85 DEG C, without using the hydrogen of molecular-weight adjusting, By molecular sieve, (ethylene is manufactured using joint Showa Corporation before it will ethylene, hexane be supplied to polymer reactor MS-3A, hexane uses the F-9 that TOSOH Co., Ltd manufactures), and triisobutyl aluminium is added with 5mmol/ hours speed Into polymerizer, in addition to this, it is polymerize by operation similarly to Example 1.

In inactivation/drying process, to the powder after polymerization steam and nitrogen mixed gas flow 20Nm³/ hour Under conditions of implement catalyst and co-catalyst inactivation.Obtained polyethylene powder uses the sieved sieve in 425 μm of aperture, will It is not removed by the powder of sieve.Polyethylene powder (PE3) is obtained in this way.Each characteristic is measured according to above-mentioned method, as a result such as table 1 It is shown.

In addition, using PE3, the method described in (5) -2 Continuous maching productivities obtains gel spinning, and comments Valence Continuous maching productivity.The obtained gel spinning is reused, the method evaluation described in (6) -2 string diameter stability Dimensional stability.In addition, the method described according to (7) acid resistance, (8) resistance to fracture of wire, carries out every evaluation.

[embodiment 5]

Using solid catalyst component [C] and as the AlMg of co-catalyst₅(C₄H₉)₁₁(OSiH)₂The organic-magnesium of expression Object is closed, in addition to this, by the way that similarly operation obtains polyethylene powder (PE4) with embodiment 4 (PE3).Similarly to Example 4 Various characteristics are measured, the results are shown in Table 1.

[embodiment 6]

Polymerization temperature is set as 70 DEG C, triisobutyl aluminium is added in polymerizer with 13mmol/ hours speed, is removed Other than this, by the way that similarly operation obtains polyethylene powder (PE5) with embodiment 4 (PE3).It measures similarly to Example 4 each Kind characteristic, the results are shown in Table 1.

[embodiment 7]

Polymerization temperature is set as 60 DEG C, in addition to this, by the way that similarly operation is polymerize with embodiment 4 (PE3).

In inactivation/drying process, to the powder after polymerization steam and nitrogen mixed gas flow 20Nm³/ hour Under conditions of implement catalyst and co-catalyst inactivation.800ppm calcium stearates are added in obtained polyethylene powder (big day chemistry corporation is made, C60), is equably mixed using Henschel mixer.Obtained polyethylene powder uses The sieved sieve in 425 μm of aperture will not removed by the powder of sieve.Polyethylene powder PE6 is obtained in this way.It is surveyed according to above-mentioned method Fixed each characteristic, the results are shown in Table 1.

In addition, using PE6, according to (5) -3 and (6) -3 record, gel piece and microporous barrier are made.It will be obtained micro- Pore membrane is assembled as the diaphragm of lead accumulator, is used as the excellent diaphragm of charge-discharge characteristic.

[comparative example 3]

In inactivation/drying process, mixed gas of the steam instead of using steam and nitrogen is used only, in addition to this, leads to The operation crossed similarly to Example 1 obtains polyethylene powder (PE7).Each characteristic is measured similarly to Example 1, as a result such as table 1 It is shown.

[comparative example 1]

In inactivation/drying process, with 10mL/ hours flow supply water instead of using the gaseous mixture of steam and nitrogen Body obtains polyethylene powder (PE8) by operation similarly to Example 1 in addition to this.It measures similarly to Example 1 each Characteristic, the results are shown in Table 1.

[comparative example 2]

In inactivation/drying process, with 10mL/ hours flow supply water instead of using the gaseous mixture of steam and nitrogen Body, in addition to this, by the way that similarly operation obtains polyethylene powder (PE9) with embodiment 6 (PE5).It surveys similarly to Example 4 Fixed each characteristic, the results are shown in Table 1.

[embodiment 9]

In inactivation/drying process, by adding methanol in flashing column come the gaseous mixture instead of using steam and nitrogen Body carries out, and in drying process obtains polyethylene powder by operation similarly to Example 1 in addition to this using only nitrogen Body (PE10).Each characteristic is measured similarly to Example 1, and the results are shown in Table 1.

[embodiment 10]

Polymerization pressure is set as 0.2MPa, in addition to this, by the way that similarly operation obtains poly- second with embodiment 4 (PE3) Alkene powder (PE11).Each characteristic is measured similarly to Example 4, and the results are shown in Table 1.

[embodiment 11]

AlMg is not used₅(C₄H₉)₁₁(OSiH)₂As co-catalyst, in addition to this, by same as embodiment 5 (PE4) Operation obtain polyethylene powder (PE12).Each characteristic is measured similarly to Example 5, and the results are shown in Table 1.

The polyethylene powder of the aluminium hydroxide of the specific dimensions containing certain number it can be seen from above, it is continuous plus Work productivity is excellent, product size excellent in stability.In addition we know, the aluminium element content of polyethylene powder be it is specific more than, by This display highly-acidproof.In addition we know, when containing specific magnesium elements amount simultaneously with specific aluminium element content, resistance to fracture of wire is excellent It is good.

In addition we know, the formed body of the polyethylene powder containing the present invention also is suitable as lithium ion battery separator, high-strength Spend fiber, lead accumulator diaphragm uses.

Industrial applicability

The present invention polyethylene powder, Continuous maching productivity is excellent, product size excellent in stability, thus lithium from The utility value of sub- battery diaphragm, lead accumulator diaphragm, the extensive purposes aspect industry such as high strength fibre is high.

Claims

1. a kind of polyethylene powder, wherein

The content for the aluminium hydroxide that the minor axis of the polyethylene powder is 50 μm or more be in polyethylene powder 500g 4 with Under, the content for the aluminium hydroxide that the minor axis is 50 μm or more is obtained by following assay methods,

The viscosity average molecular weigh of the polyethylene powder is 100000 or more, and the viscosity average molecular weigh is existed using decalin solutions 135 DEG C measurement, and

Aluminium element content is 0.2 mass ppm or more；

1) polyethylene powder 500g is put into chloroform:The volume ratio of ethyl alcohol is 3:1 chloroform and the in the mixed solvent of ethyl alcohol and divide From for the polyethylene powder of the polyethylene powder and precipitation that are floated in the in the mixed solvent,

2) using SEM-EDX, i.e. scanning electron microscope-energy dispersion type x-ray analysis equipment observes the precipitation isolated Object, and count the number for the aluminium hydroxide that minor axis is 50 μm or more.

2. polyethylene powder as described in claim 1, wherein

3. polyethylene powder as described in claim 1, wherein

Aluminium element content is 0.2 mass ppm or more, and magnesium element content is 0.5 mass ppm or more and 12 mass ppm or less.

4. application of the polyethylene powder described in claim 1 in manufacturing secondary battery membrane.

5. application as claimed in claim 4, wherein the secondary battery membrane is lithium ion secondary battery membrane.

6. a kind of microporous barrier is obtained by by polyethylene powder according to any one of claims 1 to 3 processing.

7. application of the polyethylene powder described in claim 1 in manufacturing high strength fibre.

8. a kind of high strength fibre is obtained by by polyethylene powder according to any one of claims 1 to 3 processing.